JP5016788B2 - Cellulose acylate film, polarizing plate and liquid crystal display device - Google Patents

Description

  The present invention relates to a cellulose acylate film, a polarizing plate, and a liquid crystal display device.

Liquid crystal display devices are increasingly used year by year as space-saving image display devices with low power consumption. Conventionally, the large viewing angle dependence of images has been a major drawback of liquid crystal display devices, but in recent years, high viewing angle liquid crystal modes such as VA mode and IPS mode have been put into practical use. The demand for liquid crystal display devices is rapidly expanding even in markets where viewing angles are required.
Along with this, even higher performance has begun to be required for optical compensation films and polarizing plates used in liquid crystal display devices. In particular, there is a strong demand to exhibit an optical compensation function stably with respect to changes in temperature and humidity.

  Conventional methods for imparting an optical compensation function to a polarizing plate can be roughly divided into two. First, there is a method in which an optically anisotropic layer is newly provided on a polarizing plate protective film or a retardation film is bonded together, and second, a method in which the polarizing plate protective film itself has a retardation. Conventionally, a cellulose acetate or a cellulose acetate propionate film is generally used as the polarizing plate protective film. However, these films have large dimensional changes and phase difference changes due to water absorption, and in any of these methods, there are problems such as a decrease in contrast, a reduction in viewing angle, and display unevenness due to temperature and / or humidity changes in the use environment. It was known to occur.

Conventionally, two methods have been known as means for improving this problem. The first is a method of using a polymer film having low water permeability as a polarizing plate protective film (for example, Patent Document 1), and the second is the adjustment of the elastic modulus of the upper and lower polarizing plate protective films, and the size of the polarizing plate due to temperature and humidity changes. This is a method of reducing the change (for example, Patent Document 2).
However, in the former case, the adhesion between the polarizer and the polymer film is impaired, or in the case of a polarizing plate produced by wet stretching, moisture evaporation in the drying process after polarizing plate bonding becomes insufficient, and the degree of polarization decreases. There were bad effects such as bringing about.
Further, although the latter method has a certain improvement effect under relatively mild conditions, the occurrence of display unevenness at high temperature and high humidity cannot be sufficiently suppressed.

Japanese Patent Laid-Open No. 2002-243943 JP 2003-279743 A

An object of the present invention is to provide a polarizing plate having small changes in contrast, color, and viewing angle due to heat and humidity.
Another object of the present invention is to provide a liquid crystal display device having a wide viewing angle and a high display quality without causing problems such as light leakage by using a polarizing plate having excellent viewing angle compensation capability for a liquid crystal display device. That is.
Still another object of the present invention is to provide a liquid crystal display device having a small color change depending on the viewing angle.

As a result of intensive studies, the present inventors have adjusted the relative relationship between the retardation of the cellulose acylate film used as the cell-side protective film and the retardation of the other retardation film or optically anisotropic layer. It has been found that the object of the present invention can be achieved.
That is, a cellulose acylate film containing at least one retardation increasing agent, the in-plane retardation Re and the thickness direction retardation Rth satisfy the relationship of the following formula (A), and a polarizing plate using the same And a liquid crystal display device.
(A) 30 <Rth (590) / Re (590)
(Here, Re (λ) and Rth (λ) represent Re and Rth at a wavelength of λ nm, respectively.)

  According to the present invention, it is possible to provide a polarizing plate that has a large viewing angle expansion effect, a small color change due to a viewing angle, and a small transmittance change due to heat and humidity. Furthermore, the use of a polarizing plate in which the retardation film having excellent viewing angle compensation ability and / or a protective film having low moisture permeability on both sides of the polarizer is used in a liquid crystal display device causes problems such as light leakage. Therefore, a liquid crystal display device with a wide viewing angle and high display quality can be provided.

The cellulose acylate film of the invention contains at least one retardation increasing agent, and the in-plane retardation Re and the thickness direction retardation Rth satisfy the relationship of the following formula (A).
(A) 30 <Rth (590) / Re (590)
Here, Re (λ) and Rth (λ) represent Re and Rth at the wavelength λnm, respectively.
In addition, the measuring method of Re and Rth is as having described in the Example.

The Re (590) of the cellulose acylate film of the present invention is preferably 0 nm or more and 5 nm or less, and more preferably 0 nm or more and 2 nm or less.
Rth (590) is preferably 100 nm to 400 nm, and more preferably 110 nm to 300 nm.
The Rth (590) / Re (590) ratio is preferably greater than 30, and more preferably greater than 50.
By adjusting Re (590) and Rth (590) within the above range, a film having a small contrast and color viewing angle change due to heat and humidity can be obtained. In particular, when used as a laminate with other retardation film or optically anisotropic layer, the effect is even greater.
Furthermore, it is preferable that the wavelength dispersion of Rth satisfies the relationship of the following formulas (B) and (C).
1.0 <Rth (480) / Rth (546) <2.0 (B)
0.5 <Rth (628) / Rth (546) <1.0 (C)
By using a polarizing plate in which the cellulose acylate film in which the Rth wavelength dispersion is adjusted within the above range is used as the protective film on the liquid crystal cell side, a liquid crystal display device having a small color change depending on the viewing angle can be obtained.

  The retardation of the cellulose acylate film of the present invention can be adjusted by various methods. Among these, the adjustment by the retardation increasing agent mentioned later and the adjustment by extending | stretching of a film can be used especially preferable.

(Cellulose acylate)
First, the cellulose acylate used in the present invention will be described.
The degree of substitution of cellulose acylate means the proportion of acylation of three hydroxyl groups present in cellulose structural units (glucose having β1 → 4 glycosidic bonds). The degree of substitution can be calculated by measuring the amount of bound fatty acid per unit weight of cellulose. The measurement method is carried out according to ASTM-D817-91.
The cellulose acylate of the present invention preferably has an acylation degree of 2.5 or more and 2.95 or less. The acyl group preferably has 2 to 10 carbon atoms, and particularly preferably an acetyl group, a propionyl group, or a butyryl group. In the case of cellulose acylate having only an acetyl group as an acyl group, the degree of acetylation is preferably 2.0 or more and 2.95 or less, and more preferably 2.5 or more and 2.9 or less.

When the cellulose acylate has an acetyl group and other acyl groups, the substitution degree A of the acetyl group and the substitution degree B of the acyl group having 3 or more carbon atoms are represented by the following formulas (D) and (E). It is preferable to satisfy.
(D) 2.0 ≦ A + B ≦ 3.0
(E) 0 ≦ B ≦ 1.5
The substitution degree of the acetyl group is preferably from 1 to 2.5, and more preferably from 1.5 to 2.0. As the acyl group other than the acetyl group, a propionyl group and a butyryl group are preferable.

  The cellulose acylate used in the present invention preferably has a polymerization degree of 250 to 800, more preferably a polymerization degree of 280 to 600. The cellulose acylate of the present invention preferably has a number average molecular weight of 70,000 to 230,000, more preferably a number average molecular weight of 75,000 to 230,000, and 78,000 to 120,000. Most preferably, it has a number average molecular weight of

  The cellulose acylate used in the present invention can be synthesized using an acid anhydride or acid chloride as an acylating agent. When the acylating agent is an acid anhydride, an organic acid (eg, acetic acid) or methylene chloride is used as a reaction solvent. As the catalyst, a protic catalyst such as sulfuric acid is used. When the acylating agent is an acid chloride, a basic compound is used as a catalyst. In the most common synthetic method in the industry, cellulose is an organic acid corresponding to acetyl group and other acyl groups (acetic acid, propionic acid, butyric acid) or their acid anhydrides (acetic anhydride, propionic anhydride, butyric anhydride). A cellulose ester is synthesized by esterification with a mixed organic acid component containing. In this method, cellulose such as cotton linter and wood pulp is activated with an organic acid such as acetic acid, and then esterified using a mixture of organic acid components as described above in the presence of a sulfuric acid catalyst. There are many cases to do. The organic acid anhydride component is generally used in an excess amount relative to the amount of hydroxyl groups present in the cellulose. In this esterification treatment, a hydrolysis reaction (depolymerization reaction) of the cellulose main chain β1 → 4 glycoside bond) proceeds in addition to the esterification reaction. When the hydrolysis reaction of the main chain proceeds, the degree of polymerization of the cellulose ester is lowered, and the physical properties of the cellulose ester film to be produced are lowered. Therefore, reaction conditions such as the reaction temperature must be determined in consideration of the degree of polymerization and molecular weight of the resulting cellulose ester.

In order to obtain a cellulose ester having a high degree of polymerization (high molecular weight), it is important to adjust the maximum temperature in the esterification reaction step to 50 ° C. or lower. The maximum temperature is preferably adjusted to 35 to 50 ° C, more preferably 37 to 47 ° C. When the reaction temperature is within the above range, the esterification reaction proceeds smoothly, and the degree of polymerization of the cellulose ester becomes appropriate.
After the esterification reaction, when the reaction is stopped while suppressing a temperature rise, a decrease in the degree of polymerization can be further suppressed, and a cellulose ester having a high degree of polymerization can be synthesized. That is, when a reaction terminator (eg, water, acetic acid) is added after completion of the reaction, excess acid anhydride that has not participated in the esterification reaction is hydrolyzed to form a corresponding organic acid as a by-product. This hydrolysis reaction is accompanied by intense heat generation, and the temperature in the reactor rises. When the rate of addition of the reaction terminator is high, heat is rapidly generated exceeding the cooling capacity of the reactor. For this reason, the hydrolysis reaction of the cellulose main chain may proceed remarkably and the degree of polymerization of the resulting cellulose ester may be reduced. In addition, a part of the catalyst is bonded to the cellulose during the esterification reaction, and most of the catalyst is dissociated from the cellulose during the addition of the reaction terminator. However, when the rate of addition of the reaction terminator is high, there is not enough reaction time for the catalyst to dissociate, and a part of the catalyst remains in a state of being bound to cellulose. Cellulose esters to which a strong acid catalyst is partially bonded are very poor in stability, and are easily decomposed by heat during drying of the product to lower the degree of polymerization. For these reasons, after the esterification reaction, the reaction is preferably stopped by adding a reaction terminator over a period of preferably 4 minutes or more, more preferably 4 to 30 minutes. Industrial productivity does not fall that the addition time of a reaction terminator is the said range. As the reaction terminator, water or alcohol that decomposes an acid anhydride is generally used. However, in the present invention, a mixture of water and an organic acid is preferably used as a reaction terminator in order not to precipitate triesters having low solubility in various organic solvents. When the esterification reaction is carried out under the above conditions, a high molecular weight cellulose ester having a weight average polymerization degree of 500 or more can be easily synthesized.

(Retardation raising agent)
Next, the retardation increasing agent used in the present invention will be described.
As the retardation increasing agent of the present invention, a compound having a large molecular polarizability anisotropy is preferable.
A compound represented by the following formula (I) or (II) can be particularly preferably used.

（式中、Ｘ₁は、単結合、−ＮＲ₄−、−Ｏ−または−Ｓ−であり；Ｘ₂は、単結合、−ＮＲ₅−、−Ｏ−または−Ｓ−であり；Ｘ₃は、単結合、−ＮＲ₆−、−Ｏ−または−Ｓ−であり；Ｒ¹、Ｒ²、およびＲ³は、それぞれ独立に、アルキル基、アルケニル基、芳香族環基または複素環基であり；Ｒ₄、Ｒ₅およびＲ₆は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基または複素環基である。）

Wherein X ₁ is a single bond, —NR ₄ —, —O— or —S—; X ₂ is a single bond, —NR ₅ —, —O— or —S—; X ₃ Is a single bond, —NR ₆ —, —O— or —S—; R ¹ , R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aromatic ring group or a heterocyclic group. Yes; R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.)

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁹およびＲ¹⁰はそれぞれ独立に水素原子または置換基を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁵のうち少なくとも１つは電子供与性基を表し、Ｒ⁸は水素原子、炭素数１〜４のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、炭素数６〜１２のアリール基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリールオキシ基、炭素数２〜１２のアルコキシカルボニル基、炭素数２〜１２のアシルアミノ基、シアノ基またはハロゲン原子を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group, and R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. Group, aryl group having 6 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, acylamino group having 2 to 12 carbon atoms, cyano Represents a group or a halogen atom.)

  First, the compound represented by formula (I) will be described in detail.

Wherein X ₁ is a single bond, —NR ₄ —, —O— or —S—; X ₂ is a single bond, —NR ₅ —, —O— or —S—; X ₃ Is a single bond, —NR ₆ —, —O— or —S—; R ₁ , R ₂ and R ₃ are each independently an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; ₄ , R ₅ and R ₆ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

In the formula (I), R ₁ , R ₂ , and R ₃ each independently represents an alkyl group, an alkenyl group, an aromatic ring group, or a heterocyclic group, but an aromatic ring or a heterocyclic ring is more preferable. The aromatic ring represented by each of R ₁ , R ₂ , and R ₃ is preferably phenyl or naphthyl, and particularly preferably phenyl.

R ₁ , R ₂ , and R ₃ may have a substituent on the aromatic ring or heterocyclic ring. Examples of substituents include halogen atoms, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, alkyl groups, alkenyl groups, aryl groups, alkoxy groups, alkenyloxy groups, aryloxy groups, acyloxy groups, alkoxycarbonyl groups, alkenyls. Oxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamide group, carbamoyl group, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide Groups, alkylthio groups, alkenylthio groups, arylthio groups and acyl groups.

When R ₁ , R ₂ , and R ₃ represent a heterocyclic group, the heterocyclic ring preferably has aromaticity. The heterocycle having aromaticity is generally an unsaturated heterocycle, preferably a heterocycle having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom, and particularly preferably a nitrogen atom. As the heterocyclic ring having aromaticity, a pyridine ring (2-pyridyl or 4-pyridyl as the heterocyclic group) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent described above. These substituents may be further substituted with the above substituents.

In Formula (I), X ₁ represents a single bond, —NR ₄ —, —O— or —S—, X ₂ represents a single bond, —NR ₅ —, —O— or —S—, and X ₃ Represents a single bond, —NR ₆ —, —O— or —S—. R ₄ , R ₅ and R ₆ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

The alkyl group represented by each of R ₄ , R ₅ and R ₆ may be a cyclic alkyl group or a chain alkyl group, but is preferably a chain alkyl group, rather than a chain alkyl group having a branch, A linear alkyl group is more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, further preferably 1 to 8, and 1 to 6. Is most preferred. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (for example, methoxy, ethoxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy).

The alkenyl group represented by each of R ₄ , R ₅ and R ₆ may be a cyclic alkenyl group or a chain alkenyl group, but is preferably a chain alkenyl group, more preferably than a branched chain alkenyl group. A linear alkenyl group is more preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, and 2 to 6 Most preferably. The alkenyl group may have a substituent. Examples of the substituent are the same as those of the alkyl group described above.

The aromatic ring group (aryl group) and heterocyclic group represented by R ₄ , R ₅ and R ₆ are the same as the aromatic ring and heterocyclic ring represented by R ₁ , R ₂ and R ₃ , respectively. It is the same. The aromatic ring group and the heterocyclic group may further have a substituent, and examples of the substituent are the same as those of the aromatic ring and heterocyclic ring of R ₁ , R ₂ and R ₃ .

  Preferred examples of the compound represented by the formula (I) of the present invention are shown below, but the present invention is not limited to these specific examples.

  Next, the compound of formula (II) will be described in detail.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represents an electron donating group, and R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms. A group, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom.

In the formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, Substituent T can be applied.
At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ represents an electron donating group. One of R ¹ , R ³ or R ⁵ is preferably an electron donating group, more preferably R ³ is an electron donating group.

The electron-donating group is one having a Hammett σ _p value of O or less. Rev. 91, 165 (1991). Those having a Hammett's σ _p value of 0 or less are preferably applicable, and those having −0.85 to 0 are more preferably used. Examples thereof include an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.
The electron donating group is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 6 carbon atoms). 1 to 4 carbon atoms.

R ¹ is preferably a hydrogen atom or an electron donating group, more preferably an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, and still more preferably an alkyl group having 1 to 4 carbon atoms or a carbon number 1 to 12 Particularly preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred is a methoxy group.

R ² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably a carbon number). 1 to 4, more preferably a methyl group), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to carbon atoms). 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group.

R ³ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, still more preferably an alkyl group or an alkoxy group, particularly preferably. An alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). Most preferred are n-propoxy group, ethoxy group, and methoxy group

R ⁴ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, and still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms), particularly preferably. Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and most preferably a hydrogen atom, a methyl group, or a methoxy group.

Preferred groups for R ⁵ are the same as those listed for R ² .

R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom, more preferably a hydrogen atom or a halogen atom. More preferably a hydrogen atom.

R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Represents an aryloxy group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom, and may have a substituent if possible. The substituent T described later can be applied as the substituent.
R ⁸ is preferably an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryloxy group having 2 to 12 carbon atoms. And more preferably an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms), and particularly preferably a methoxy group, an ethoxy group, and n. -A propoxy group, an iso-propoxy group, and an n-butoxy group.

  Of the formula (II), the following formula (II-A) is more preferable.

(In the formula (II-A), R ¹¹ represents an alkyl group. R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a substituent. R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 12 carbon atoms. An aryloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom, and R ¹¹ represents an alkyl group.)

In formula (II-A), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as those in formula (II), and preferred ranges Is the same.

In formula (II-A), R ¹¹ represents an alkyl group, and the alkyl group represented by R ¹¹ may be linear or branched, and may further have a substituent. An alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group and the like).

  Of the formula (II), the following formula (II-B) is more preferable.

(In formula (II-B), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, and R ¹¹ represents the number of carbon atoms. Represents an alkyl group having 1 to 12. X is an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 carbon atoms. -12 represents an aryloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom.)

In formula (II-B), R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ have the same meanings as those in formula (II), and the preferred ranges are also the same. .
In formula (II-B), R ¹¹ has the same meaning as that in formula (II-A), and the preferred range is also the same.

In formula (II-B), X is an alkyl group having 1 to 4 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 6 carbon atoms. 12 an aryloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acylamino group having 2 to 12 carbon atoms, a cyano group, or a halogen atom.
When all of R ¹ , R ² , R ⁴ and R ⁵ are hydrogen atoms, X is preferably an alkyl group, alkynyl group, aryl group, alkoxy group or aryloxy group, more preferably an aryl group or alkoxy group. And an aryloxy group, more preferably an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms). And particularly preferably a methoxy group, a methoxy group, an n-propoxy group, an iso-propoxy group or an n-butoxy group.

When at least one of R ¹ , R ² , R ⁴ and R ⁵ is a substituent, X is preferably an alkynyl group, aryl group, alkoxycarbonyl group or cyano group, more preferably an aryl group (preferably 6 to 12 carbon atoms), a cyano group, and an alkoxycarbonyl group (preferably 2 to 12 carbon atoms), more preferably an aryl group (preferably an aryl group having 6 to 12 carbon atoms, more preferably a phenyl group, p-cyanophenyl group and p-methoxyphenyl group), alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, still more preferably having 2 to 4 carbon atoms, particularly preferably methoxycarbonyl, Ethoxycarbonyl, n-propoxycarbonyl), cyano group, particularly preferably phenyl group, methoxycarbonyl. Boniru group, an ethoxycarbonyl group, n- propoxycarbonyl group, a cyano group.

  Of the formula (II), the following formula (II-C) is more preferable.

In formula (II-C), R ¹ , R ² , R ⁴ , R ⁵ , R ¹¹ and X have the same meanings as those in formula (II-B), and preferred ranges are also the same. )

  Among the compounds represented by the formula (II), a compound represented by the following formula (II-D) is preferable.

(In the formula (II-D), R ² , R ⁴ and R ⁵ have the same meanings as those in the formula (II-C), and the preferred ranges are also the same. R ²¹ and R ²² each independently represents the number of carbon atoms. X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group.

R ²¹ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an ethyl group or a methyl group.
R ²² represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

X ¹ is an aryl group having 6 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or a cyano group, preferably an aryl group having 6 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a cyano group. More preferably a phenyl group, a p-cyanophenyl group, a p-methoxyphenyl group, a methoxycarbonyl, an ethoxycarbonyl, an n-propoxycarbonyl, a cyano group, and still more preferably a phenyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group and cyano group.

  Most preferred among the formulas (II) is the following formula (II-E).

(In the formula (II-E), R ² , R ⁴ and R ⁵ have the same meanings as those in the formula (II-D), and the preferred range is also the same, but one of them is represented by —OR ^13. (R ¹³ is an alkyl group having 1 to 4 carbon atoms.) R ²¹ , R ²² and X ¹ have the same meanings as those in formula (II-D), and preferred ranges are also the same. )

In formula (II-E), R ² , R ⁴ and R ⁵ have the same meanings as those in formula (II-D), and the preferred range is also the same, but one of them is a group represented by —OR ^13. (R ¹³ is an alkyl group having 1 to 4 carbon atoms), preferably R ⁴ and R ⁵ are groups represented by —OR ¹³ , more preferably R ⁴ is represented by —OR ^13. It is a group.
R ¹³ represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group or a methyl group, and still more preferably a methyl group.

The aforementioned substituent T will be described below.
Examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, and n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number). 2 to 8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number). 2-8, for example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6-30 carbon atoms) More preferably from 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p- methylphenyl, naphthyl and the like.),

  A substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino; And an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like.) An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy), an acyl group. (Preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Zoyl, formyl, pivaloyl, etc.), alkoxycarbonyl groups (preferably having 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc. An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl). An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy).

  An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetylamino and benzoylamino), an alkoxycarbonylamino group (preferably Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and an aryloxycarbonylamino group (preferably 7 to 7 carbon atoms). 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and the like, sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably carbon atoms) 1 to 16, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino Such as benzenesulfonylamino and the like.),

  Sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms. Examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc. ),

  An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably having 6 carbon atoms). -20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), alkylsulfonyl group or arylsulfonyl group (preferably 1 to 20 carbon atoms, more preferably Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl.), An alkylsulfinyl group or an arylsulfinyl group (preferably having a carbon number of 1 to 20, more preferably a carbon number). 1 to 16, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfur And ureido groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.). And phosphoric acid amide groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide). ),

  Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic ring A group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino Benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

  Specific examples of the compound represented by formula (II) will be described below in detail, but the present invention is not limited to the following specific examples.

The compound represented by the formula (II) used in the present invention can be synthesized by a general ester reaction of a substituted benzoic acid and a phenol derivative, and any reaction may be used as long as it is an ester bond forming reaction. Examples thereof include a method of converting a substituted benzoic acid to an acid halide and then condensing with phenol, a method of dehydrating the substituted benzoic acid and a phenol derivative using a condensing agent or a catalyst, and the like.
In view of the production process and the like, a method in which the substituted benzoic acid is functionally converted to an acid halide and then condensed with phenol is preferable.

  Reaction solvents include hydrocarbon solvents (preferably toluene and xylene), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), ketone solvents, ester solvents, acetonitrile, dimethylformamide, dimethyl Acetamide or the like can be used. These solvents may be used alone or in admixture of several kinds, and preferred reaction solvents are toluene, acetonitrile, dimethylformamide and dimethylacetamide.

The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.
In this reaction, it is preferable not to use a base. When a base is used, either an organic base or an inorganic base may be used, preferably an organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine and the like).

  The method for synthesizing the compound of the present invention is specifically described below, but the present invention is not limited by the following specific examples.

[Synthesis Example 1: Synthesis of Exemplified Compound A-1]
After heating 24.6 g (0.116 mol) of 3,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of NN-dimethylformamide to 60 ° C., 15.2 g (0.127 mol) of thionyl chloride was slowly added. And then heated at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 15.1 g (0.127 mol) of 4-cyanophenol in 50 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 60 ° C. for 3 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and water. After removing water from the obtained organic phase with sodium sulfate, the solvent was distilled off under reduced pressure. 100 mL was added and recrystallization operation was performed. The acetonitrile solution was cooled to room temperature, and the precipitated crystals were collected by filtration to obtain 11.0 g (yield 11%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.50 (br, 9H), 7.37 (d, 2H), 7.45 (s, 2H), 7.77 (s, 2H)
Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 172 to 173 ° C.

[Synthesis Example 2: Synthesis of Exemplified Compound A-2]
After heating 106.1 g (0.5 mol) of 2,4,5-trimethoxybenzoic acid, 340 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 65.4 g (0.55 mol) of thionyl chloride was slowly added dropwise, Heated at 65-70 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 71.5 g (0.6 mol) of 4-cyanophenol in 150 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 80 to 85 ° C. for 2 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate (1 L) and water. After removing water from the obtained organic phase with magnesium sulfate, about 500 mL of the solvent was distilled off under reduced pressure, and 1 L of methanol was added. And recrystallization operation was performed. The precipitated crystals were collected by filtration to obtain 125.4 g (yield 80%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.91 (s, 3H), 3.93 (s, 3H), 3.98 (s, 3H), 6.59 (s, 1H), 7.35 (d, 2H), 7.58 (s, 1H), 7.74 (d, 2H)
Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 116 ° C.

[Synthesis Example 3: Synthesis of Exemplified Compound A-3]
After heating 10.1 g (47.5 mmol) of 2,3,4-trimethoxybenzoic acid, 40 mL of toluene and 0.5 mL of dimethylformamide to 80 ° C., 6.22 g (52.3 mmol) of thionyl chloride was slowly added dropwise. And heated and stirred at 80 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 6.2 g (52.3 mmol) of 4-cyanophenol in 20 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 80 to 85 ° C. for 2 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and water. After removing water from the obtained organic phase with sodium sulfate, the solvent was distilled off under reduced pressure, 50 mL of methanol was added, and recrystallization operation was performed. Went. The precipitated crystals were collected by filtration to obtain 11.9 g (yield 80%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ): δ 3.50 (br, 9H), 7.37 (d, 2H), 7.45 (s, 2H), 7.77 (s, 2H)
Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 102 to 103 ° C.

[Synthesis Example 4: Synthesis of Exemplary Compound A-4]
After heating 25.0 g (118 mmol) of 2,4,6-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 15.4 g (129 mmol) of thionyl chloride was slowly added dropwise, Stir for hours. Thereafter, a solution prepared by previously dissolving 15.4 g (129 mmol) of 4-cyanophenol in 50 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 80 to 85 ° C. for 4.5 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and water. After removing water from the obtained organic phase with sodium sulfate, the solvent was distilled off under reduced pressure, and 500 mL of methanol and 100 mL of acetonitrile were added, Recrystallization operation was performed. The precipitated crystals were collected by filtration to obtain 10.0 g (yield 27%) of the target compound as white crystals. The compound was identified by mass spectrum.
Mass spectrum: m / z 314 (M + H) ⁺
The melting point of the obtained compound was 172 to 173 ° C.

[Synthesis Example 5: Synthesis of Exemplary Compound A-5]
After heating 15.0 g (82.3 mmol) of 2,3-dimethoxybenzoic acid, 60 mL of toluene and 0.5 mL of dimethylformamide to 60 ° C., 10.7 (90.5 mmol) of thionyl chloride was slowly added dropwise. The mixture was heated and stirred at 60 ° C. for 2 hours. Thereafter, a solution prepared by previously dissolving 10.8 g (90.5 mmol) of 4-cyanophenol in 30 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 70 to 80 ° C. for 7 hours. After cooling the reaction solution to room temperature, 90 mL of isopropyl alcohol was added, and the precipitated crystals were collected by filtration to obtain 12.3 g (yield 53%) of the target compound as white crystals. The compound was identified by mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 104 ° C.

[Synthesis Example 6: Synthesis of Exemplified Compound A-6]
The synthesis was performed in the same manner except that 2,3-dimethoxybenzoic acid in A-5 was changed to 2,4-dimethoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 134 to 136 ° C.

[Synthesis Example 7: Synthesis of Exemplified Compound A-7]
After heating 25.0 g (137 mmol) of 2,5-dimethoxybenzoic acid, 100 mL of toluene and 1.0 mL of dimethylformamide to 60 ° C., 18.0 (151 mmol) of thionyl chloride was slowly added dropwise. Stir for hours. Thereafter, a solution prepared by previously dissolving 18.0 g (151 mmol) of 4-cyanophenol in 50 mL of acetonitrile was slowly added dropwise. After completion of the addition, the mixture was heated and stirred at 70 to 80 ° C. for 7.5 hours. After cooling the reaction solution to room temperature, liquid separation operation was performed with ethyl acetate and saturated brine, and water was removed from the obtained organic phase with sodium sulfate. Then, the solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane -Purification operation with ethyl acetate (9/1, V / V)) yielded 18.8 g (yield 48%) of the target compound as white crystals. The compound was identified by mass spectrum.

Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 79-80 ° C.

[Synthesis Example 8: Synthesis of Exemplary Compound A-8]
The synthesis was performed in the same manner except that 2,3-dimethoxybenzoic acid in A-5 was changed to 2,6-dimethoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 284 (M + H) ⁺
The melting point of the obtained compound was 130 to 131 ° C.

[Synthesis Example 9: Synthesis of Exemplary Compound A-11]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 was changed to 76.9 g of 4-chlorophenol. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.90 (s, 3H), 3.94 (s, 3H), 3.99 (s, 3H), 6.58 (s, 1H), 7.15 (d, 2H), 7.37 (d, 2H), 7.56 (s, 1H)
Mass spectrum: m / z 323 (M + H) ⁺
The melting point of the obtained compound was 127 to 129 ° C.

[Synthesis Example 10: Synthesis of Exemplified Compound A-12]
After heating 45.0 g (212 mmol) of 2,4,5-trimethoxybenzoic acid, 180 mL of toluene and 1.8 mL of dimethylformamide to 60 ° C., 27.8 g (233 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 2.5 hours. Thereafter, a solution prepared by previously dissolving 35.4 g (233 mmol) of methyl 4-hydroxybenzoate in 27 mL of dimethylformamide was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. 270 mL was added, and the precipitated crystals were collected by filtration to obtain 64.5 g (yield 88%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.95 (m, 9H), 3.99 (s, 3H), 6.57 (s, 1H), 7.28 (d, 2H), 7.57 (s, 1H) 8.11 (d, 2H)
Mass spectrum: m / z 347 (M + H) ⁺
The melting point of the obtained compound was 121 to 123 ° C.

[Synthesis Example 11: Synthesis of Exemplary Compound A-13]
After heating 20.0 g (94.3 mmol) of 2,4,5-trimethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 12.3 g (104 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 3.5 hours. Thereafter, a solution prepared by previously dissolving 17.7 g (104 mmol) of 4-phenylphenol in 150 mL of toluene was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was then cooled to room temperature, and 250 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 21.2 g (yield 62%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.93 (s, 3H), 3.96 (s, 3H), 3.99 (s, 3H), 6.59 (s, 1H), 7.26-7. 75 (m, 10H)
Mass spectrum: m / z 365 (M + H) ⁺
The melting point of the obtained compound was 131-132 ° C.

[Synthesis Example 12: Synthesis of Exemplified Compound A-14]
After heating 12.9 g (61 mmol) of 2,4,5-trimethoxybenzoic acid, 50 mL of toluene, and 0.6 mL of dimethylformamide to 60 ° C., 8.0 g (67 mmol) of thionyl chloride was slowly added dropwise to the mixture at 60 ° C. And stirred for 3.5 hours. Thereafter, a solution prepared by previously dissolving 17.7 g (104 mmol) of 4-phenylphenol in 25 mL of acetonitrile was slowly added, and the mixture was heated and stirred at 80 ° C. for 3 hours. The reaction solution was then cooled to room temperature, and 100 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 21.6 g (yield 93%) of the target compound as white crystals. The compound was identified by mass spectrum.
Mass spectrum: m / z 381 (M + H) ⁺
The melting point of the obtained compound was 91-92 ° C.

[Synthesis Example 13: Synthesis of Exemplary Compound A-15]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 was changed to 56.4 g of phenol. The compound was identified by ¹ H-NMR and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.91 (s, 3H), 3.93 (s, 3H), 3.99 (s, 3H), 6.58 (s, 1H), 7.19-7. 27 (m, 3H), 7.42 (m, 2H), 7.58 (s, 1H)
Mass spectrum: m / z 365 (M + H) ⁺
The melting point of the obtained compound was 105 to 108 ° C.
Mass spectrum: m / z 289 (M + H) ⁺

[Synthesis Example 14: Synthesis of Exemplified Compound A-16]
The target compound can be obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 is changed to 74.4 g of 4-methoxyphenol. The compound was identified by ¹ H-NMR and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 3.84 (s, 3H), 3.92 (s, 3H), 3.93 (s, 3H), 3.99 (s, 3H), 6.58 (s, 1H), 6.92 (d, 2H), 7.12 (d, 2H), 7.42 (m, 2H), 7.58 (s, 1H)
Mass spectrum: m / z 319 (M + H) ⁺
The melting point of the obtained compound was 102 to 103 ° C.

[Synthesis Example 15: Synthesis of Exemplified Compound A-17]
The target compound was obtained in the same manner except that 71.5 g of 4-cyanophenol in A-2 was changed to 73.3 g of 4-ethylphenol. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
Mass spectrum: m / z 317 (M + H) ⁺
The melting point of the obtained compound was 70 to 71 ° C.

[Synthesis Example 16: Synthesis of Exemplary Compound A-24]
After heating 27.3 g (164 mmol) of 4-ethoxybenzoic acid, 108 mL of toluene, and 1 mL of dimethylformamide to 60 ° C., 21.5 g (181 mmol) of thionyl chloride was slowly added dropwise, followed by heating and stirring at 60 ° C. for 2 hours. . Thereafter, a solution in which 25.0 g (181 mmol) of 4-ethoxyphenol was previously dissolved in 50 mL of acetonitrile was slowly added, and the mixture was heated and stirred at 80 ° C. for 4 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. The precipitated crystals were collected by filtration to obtain 30.6 g (yield 65%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 1.48-1.59 (m, 6H), 4.05 (q, 2H), 4.10 (q, 2H), 6.89-7.00 (m, 4H) ), 7.10 (d, 2H), 8.12 (d, 2H)
Mass spectrum: m / z 287 (M + H) ⁺
The melting point of the obtained compound was 113 to 114 ° C.

[Synthesis Example 17: Synthesis of Exemplified Compound A-25]
After heating 24.7 g (149 mmol) of 4-ethoxybenzoic acid, 100 mL of toluene and 1 mL of dimethylformamide to 60 ° C., 19.5 g (164 mmol) of thionyl chloride was slowly added dropwise, and the mixture was heated and stirred at 60 ° C. for 2 hours. . Then, after slowly adding a solution prepared by dissolving 25.0 g (165 mmol) of 4-propoxyphenol in 50 mL of acetonitrile in advance and heating and stirring at 80 ° C. for 4 hours, the reaction solution was cooled to room temperature, and then 100 mL of methanol was added. The precipitated crystals were collected by filtration, 100 mL of methanol was added to the obtained solid, and recrystallization was performed. The obtained crystals were collected by filtration to obtain 33.9 g (yield 76%) of the target compound as white crystals. It was. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.

¹ H-NMR (CDCl ₃ ) δ 1.04 (t, 3H), 1.45 (t, 3H), 1.82 (q, 2H), 3.93 (q, 2H), 4.04 (q, 2H), 6.89-7.00 (m, 4H), 7.10 (d, 2H), 8.12 (d, 2H)
Mass spectrum: m / z 301 (M + H) ⁺
The melting point of the obtained compound was 107 ° C.

[Synthesis Example 18: Synthesis of Exemplified Compound A-27]
The compound was synthesized in the same manner except that 27.3 g of 4-ethoxybenzoic acid in the synthesis method of A-24 was changed to 29.5 g of 4-propoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 301 (M + H) ⁺
The melting point of the obtained compound was 88-89 ° C.

[Synthesis Example 19: Synthesis of Exemplary Compound A-28]
The compound was synthesized in the same manner except that 24.7 g of 4-ethoxybenzoic acid in the synthesis method of A-25 was changed to 26.8 g of 4-propoxybenzoic acid. The compound was identified by mass spectrum.
Mass spectrum: m / z 315 (M + H) ⁺
The melting point of the obtained compound was 92 ° C.

[Synthesis Example 20: Synthesis of Exemplified Compound A-40]
After heating 20.0 g (109 mmol) of 2,4-dimethoxybenzoic acid, 80 mL of toluene, and 0.8 mL of dimethylformamide to 60 ° C., 14.4 g (121 mmol) of thionyl chloride was slowly added dropwise, The mixture was heated and stirred for 5 hours. Thereafter, a solution prepared by previously dissolving 20.5 g (121 mmol) of 4-phenylphenol in 50 mL of dimethylformamide was slowly added and stirred at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 100 mL of methanol was added. In addition, the precipitated crystals were collected by filtration to obtain 31.7 g (yield 86%) of the target compound as white crystals. The compound was identified by mass spectrum.
Mass spectrum: m / z 335 (M + H) ⁺
The melting point of the obtained compound was 161-162 ° C.

[Synthesis Example 21: Synthesis of Exemplified Compound A-42]
After heating 30.0 g (165 mmol) of 2,4-dimethoxybenzoic acid, 120 mL of toluene, and 1.2 mL of dimethylformamide to 60 ° C., 21.6 g (181 mmol) of thionyl chloride was slowly added dropwise. Stir for hours. Thereafter, a solution prepared by previously dissolving 27.6 g (181 mmol) of methyl 4-fluorohydroxybenzoate in 40 mL of dimethylformamide was slowly added, and the mixture was heated and stirred at 80 ° C. for 6 hours, and then the reaction solution was cooled to room temperature. Methanol (140 mL) was added, and the precipitated crystals were collected by filtration to obtain 24.4 g (yield 47%) of the target compound as white crystals. The compound was identified by ¹ H-NMR (400 MHz) and mass spectrum.
¹ H-NMR (CDCl ₃ ) δ 3.92 (m, 9H), 6.56 (m, 2H), 7.27 (m, 2H), 8.09 (m, 3H)

Mass spectrum: m / z 317 (M + H) ⁺
The melting point of the obtained compound was 122-123 ° C.

  As the retardation increasing agent of the present invention, a compound represented by the following formula (III) is also preferable. Hereinafter, the compound of the formula (III) will be described in detail.

（式中、Ａｒ¹およびＡｒ³はそれぞれ独立にアリール基または一価芳香族ヘテロ環基を表し、Ａｒ²はアリーレン基または二価芳香族へテロ環基を表し、Ｌ¹およびＬ²はそれぞれ独立に単結合または２価の連結基を表し、ｎは３以上の整数を表し、また、それぞれＡｒ²とＬ²は同一であっても異なっていてもよい。）

(In the formula, Ar ¹ and Ar ³ each independently represents an aryl group or a monovalent aromatic heterocyclic group, Ar ² represents an arylene group or a divalent aromatic heterocyclic group, and L ¹ and L ² each represent Independently represents a single bond or a divalent linking group, n represents an integer of 3 or more, and Ar ² and L ² may be the same or different, respectively.

In formula (III), Ar ¹ and Ar ³ each independently represent an aryl group or a monovalent aromatic heterocyclic group, Ar ² represents an arylene group or a divalent aromatic heterocyclic group, Ar ² may be all the same or different.
In the formula (III), the aryl group represented by Ar ¹ or Ar ³ is preferably an aryl group having 6 to 30 carbon atoms, which may be a single ring or may form a condensed ring with another ring. May be. Further, if possible, it may have a substituent, and the substituent T ′ described later can be applied as the substituent. More preferably, the aryl group represented by Ar ¹ or Ar ³ has 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms. For example, a phenyl group, a 2,4-dialkoxyphenyl group, 2, 4, 5 -A trialkoxyphenyl group, a naphthyl group, etc. are mentioned.
In the formula (III), the arylene group represented by Ar ² is preferably an arylene group having 6 to 30 carbon atoms, which may be a single ring or may form a condensed ring with another ring. . Further, if possible, it may have a substituent, and the substituent T described later can be applied as the substituent. The arylene group represented by Ar ² preferably has 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylene group, a methylphenylene group, a methoxyphenylene group, and a naphthylene group.

In formula (III), the monovalent aromatic heterocyclic group represented by Ar ¹ or Ar ³ has one hydrogen atom removed from the aromatic heterocyclic ring containing at least one of an oxygen atom, a nitrogen atom or a sulfur atom. It is preferably a monovalent group, more preferably a monovalent aromatic heterocyclic group containing at least one of a 5- to 6-membered oxygen atom, nitrogen atom or sulfur atom. Moreover, you may have a substituent further if possible. Substituent T ′ described later can be applied as the substituent.
In formula (III), the divalent aromatic heterocyclic group represented by Ar ² is a divalent group obtained by removing one hydrogen atom from the monovalent aromatic heterocyclic group represented by Ar ¹ or Ar ^3. It is preferable.

In the formula (III), specific examples of the aromatic heterocycle represented by Ar ¹ , Ar ² or Ar ³ include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, Indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, Examples include benzthiazole, benzotriazole, tetrazaindene, pyrrolotriazole, and pyrazolotriazole. Among them, preferred as the aromatic heterocycle are benzimidazole, benzoxazole, benzthiazole, and benzotriazole.

In formula (III), L ¹ and L ² each independently represents a single bond or a divalent linking group. L ¹ and L ² may be the same or different. Further, all L ² in the repeating unit may be the same or different.
Preferred as the divalent linking group are —O—, —NR— (R represents a hydrogen atom or an optionally substituted alkyl group or aryl group), —CO—, —SO ₂ —, — S-, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a group obtained by combining two or more of these divalent groups, more preferably -O-, -NR —, —CO—, —SO ₂ NR—, —NRSO ₂ —, —CONR—, —NRCO—, —COO—, —OCO—, —OCOO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) _2- and alkynylene groups. R preferably represents a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.

In the compound represented by the formula (III) of the present invention, Ar ² binds to L ¹ and L ² , but when Ar ² is a phenylene group, L ¹ -Ar ² -L ² and L ² -Ar ² -L ² are most preferably in the relation of mutually para position (1,4-position).

  In formula (III), n represents an integer greater than or equal to 3, Preferably it is 3-7, More preferably, it is 3-6, More preferably, it is 3-5.

  Of the compounds of the formula (III), compounds represented by the following formula (III-A) can be preferably used.

（式中、Ｒ²、Ｒ⁴、Ｒ⁵はそれぞれ独立に水素原子または置換基を表し、Ｒ¹¹、Ｒ¹²はそれぞれ独立に水素原子またはアルキル基を表し、Ｌ²、Ｌ³はそれぞれ独立に単結合または二価の連結基を表し、Ａｒ²はアリーレン基または二価芳香族へテロ環基を表し、Ａｒ³はアリール基または一価芳香族へテロ環基を表し、ｎは３以上の整数を表し、また、ｎ種存在するＬ²、Ａｒ²はそれぞれ同一であっても異なっていてもよい。ただし、Ｒ¹¹、Ｒ¹²は互いに異なっており、Ｒ¹²で表されるアルキル基はへテロ原子を含まない。）

(Wherein R ² , R ⁴ and R ⁵ each independently represents a hydrogen atom or a substituent, R ¹¹ and R ¹² each independently represents a hydrogen atom or an alkyl group, and L ² and L ³ each independently represent A single bond or a divalent linking group, Ar ² represents an arylene group or a divalent aromatic heterocyclic group, Ar ³ represents an aryl group or a monovalent aromatic heterocyclic group, and n is 3 or more. N ² kinds of L ² and Ar ² may be the same or different, provided that R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² is Does not contain heteroatoms.)

In formula (III-A), Ar ² , Ar ³ and L ² have the same meanings as those in formula (III), and preferred ranges are also the same. L ³ represents a single bond or a divalent linking group, and is synonymous with the single bond or divalent linking group of L ¹ and L ² in Formula (III), and the preferred range is also the same.

In formula (III-A), R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, and the substituent T described below can be applied to the substituent.

R ² is preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably a carbon number). 1 to 4, more preferably a methyl group), an alkoxy group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to carbon atoms). 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group, and most preferred is a hydrogen atom.

R ⁴ is preferably a hydrogen atom or an electron donating group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or a hydroxyl group, and still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms), particularly preferably. Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and most preferably a hydrogen atom or a methoxy group.

R ⁵ is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group or an alkoxy group, still more preferably a hydrogen atom or an alkyl group (preferably Is a C1-C4, more preferably a methyl group), an alkoxy group (preferably C1-C12, more preferably C1-C8, still more preferably C1-C6, particularly preferably carbon Equations 1 to 4). Particularly preferred are a hydrogen atom, a methyl group and a methoxy group. Most preferably, it is a hydrogen atom.

R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group, R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² does not contain a hetero atom. Here, the hetero atom means an atom other than a hydrogen atom or a carbon atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus, silicon, a halogen atom (F, Cl, Br, I), and boron.
The alkyl group represented by R ¹¹ and R ¹² is a linear, branched, or cyclic alkyl group that is a substituted or unsubstituted alkyl group, preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (that is, a monovalent structure in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms) And a tricyclo structure having more ring structures.

Preferred examples of the alkyl group represented by R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. , Iso-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group 2-hexyldecyl group, cyclohexyl group, cycloheptyl group, 2-hexenyl group, oleyl group, linoleyl group, linolenyl group and the like. Examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, and 4-n-dodecylcyclohexyl group. Examples of the bicycloalkyl group include a bicyclo [1,2,2] heptan-2-yl group and a bicyclo [2 , 2, 2] octane-3-yl group and the like.

R ¹¹ is more preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, or isopropyl group, particularly preferably a hydrogen atom or methyl group, and most preferably a methyl group.
R ¹² is particularly preferably an alkyl group containing 2 or more carbon atoms, and more preferably an alkyl group containing 3 or more carbon atoms. Those having a branched or cyclic structure are particularly preferably used.

Hereinafter, specific examples of the alkyl group represented by R ¹² will be described. However, the present invention is not limited to the following specific examples.

In the above examples, # means the oxygen atom side.
In formula (III-A), n represents an integer of 3 or more, preferably 3 to 7, more preferably 3 to 6, and further preferably 3 to 5.

  Of the compounds of the formula (III-A), compounds represented by the following formulas (III-B) and (III-C) can be more preferably used.

（式中、Ｒ²、Ｒ⁵はそれぞれ独立に水素原子または置換基を表し、Ｒ¹¹、Ｒ¹²はそれぞれ独立に水素原子またはアルキル基を表し、Ｌ²、Ｌ³はそれぞれ独立に単結合または二価の連結基を表し、Ａｒ²はアリーレン基または二価芳香族へテロ環基を表し、Ａｒ³はアリール基または一価芳香族へテロ環基を表し、ｎは３以上の整数を表し、また、ｎ種存在するＬ²、Ａｒ²はそれぞれ同一であっても異なっていてもよい。ただしＲ¹¹、Ｒ¹²は互いに異なっており、Ｒ¹²で表されるアルキル基はへテロ原子を含まない。）

(Wherein R ² and R ⁵ each independently represent a hydrogen atom or a substituent, R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group, and L ² and L ³ each independently represent a single bond or Represents a divalent linking group, Ar ² represents an arylene group or a divalent aromatic heterocyclic group, Ar ³ represents an aryl group or a monovalent aromatic heterocyclic group, and n represents an integer of 3 or more. In addition, n types of L ² and Ar ² may be the same or different, provided that R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² represents a hetero atom. Not included.)

In formula (III-B), R ² , R ⁵ , R ¹¹ , R ¹² , and n have the same meanings as those in formula (III-A), and preferred ranges are also the same. L ² , L ³ , Ar ² and Ar ³ have the same meanings as those in formula (III-A), and preferred ranges are also the same.

（式中、Ｒ²、Ｒ⁵はそれぞれ独立に水素原子または置換基を表し、Ｒ¹¹、Ｒ¹²、Ｒ¹³はそれぞれ独立に水素原子またはアルキル基を表し、Ｌ²、Ｌ³はそれぞれ独立に単結合または二価の連結基を表す。Ａｒ²はアリーレン基または二価芳香族へテロ環基を表し、Ａｒ³はアリール基または一価芳香族へテロ環基を表し、ｎは３以上の整数を表し、また、ｎ種存在するＬ²、Ａｒ¹はそれぞれ同一であっても異なっていてもよい。ただしＲ¹¹、Ｒ¹²は互いに異なっており、Ｒ¹²で表されるアルキル基はへテロ原子を含まない。）

(In the formula, R ² and R ⁵ each independently represent a hydrogen atom or a substituent, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group, and L ² and L ³ each independently represent Represents a single bond or a divalent linking group, Ar ² represents an arylene group or a divalent aromatic heterocyclic group, Ar ³ represents an aryl group or a monovalent aromatic heterocyclic group, and n is 3 or more. N ² types of L ² and Ar ¹ may be the same or different, provided that R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² is (Does not contain terror atoms.)

In formula (III-C), R ² , R ⁵ , R ¹¹ , R ¹² , and n have the same meanings as those in formula (III-A), and the preferred ranges are also the same. L ² , L ³ , Ar ² and Ar ³ have the same meanings as those in formula (III-A), and preferred ranges are also the same.
R ¹³ represents a hydrogen atom or an alkyl group. As the alkyl group, alkyl groups shown as preferred examples of R ¹¹ and R ¹² are preferably used. Preferably, it represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group. R ¹¹ and R ¹³ may be the same or different, but both are particularly preferably methyl groups.

  Of the compounds of the formula (III), compounds represented by the following formula (IV) can be used more preferably.

（式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶はそれぞれ独立に水素原子またはアルキル基を表し、Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴はそれぞれ独立に水素原子または置換基を表し、Ａｒ⁴はアリーレン基または二価芳香族ヘテロ環基を表し、Ｌ³およびＬ⁴はそれぞれ独立に単結合または２価の連結基を表し、ｎは３以上の整数を表し、また、それぞれＡｒ⁴とＬ⁴は同一であっても異なっていても良い。）

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group, and R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom. Or Ar ⁴ represents an arylene group or divalent aromatic heterocyclic group, L ³ and L ⁴ each independently represent a single bond or a divalent linking group, and n represents an integer of 3 or more. In addition, Ar ⁴ and L ⁴ may be the same or different, respectively.

In the formula (IV), R ¹¹ , R ¹² and R ¹³ have the same meanings as those in the formula (III-C), and R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meanings as R ¹¹ , R ¹² and R ¹³ , respectively. There are also preferred ranges. R ²¹ , R ²² , R ²³ and R ²⁴ have the same meanings as R ² and R ⁵ in formula (III-A), and the preferred ranges are also the same. L ³ has the same meaning as L ³ in formula (III-C), preferred ranges are also the same. L ⁴ , Ar ⁴ and n have the same meanings as L ² , Ar ² and n in formula (III), and preferred ranges are also the same.

  Of the compounds of the formula (IV), compounds represented by the following formula (V) can also be used more preferably.

(In Formula (V), R ²¹ and R ²² each independently represent a hydrogen atom or a substituent, R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group, and L ³ and L ⁴ each independently represent Represents a single bond or a divalent linking group, Ar ⁴ represents an arylene group or a divalent aromatic heterocyclic group, n represents an integer of 3 or more, and L ⁴ and Ar ⁴ may be the same (However, R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² does not include a hetero atom.)

In the formula (V), R ¹¹ , R ¹² , R ²¹ , R ²² , L ³ , L ⁴ , Ar ⁴ and n have the same meanings as those in the formula (IV), and preferred ranges are also the same. However, R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² does not contain a hetero atom.

  Of the compounds of the formula (IV), compounds represented by the following formula (VI) can be particularly preferably used.

(In the formula (VI), R ²¹ and R ²² each independently represents a hydrogen atom or a substituent, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group, and L ³ and L ⁴ represent Each independently represents a single bond or a divalent linking group, Ar ⁴ represents an arylene group or a divalent aromatic heterocyclic group, n represents an integer of 3 or more, and L ⁴ and Ar ⁴ are the same. (However, R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² does not include a hetero atom.)

In formula (VI), R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , L ³ , L ⁴ , Ar ⁴ , and n have the same meanings as those in formula (IV), and preferred ranges are also the same. . However, R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² does not contain a hetero atom.

The substituent T ′ in the above formulas (III) to (VI) will be described below.
The substituent T ′ is preferably a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. , Isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom is removed from a bicycloalkane having 5 to 30 carbon atoms. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane -3-yl), an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group or an allyl group), a cycloalkenyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms). Substituted cycloalkenyl groups, that is, monovalent groups in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicyclo Alkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-ene-4- ), An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or a propargyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) A phenyl group, a p-tolyl group, a naphthyl group, a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, aromatic or non-aromatic heterocyclic compound with one hydrogen atom removed. A 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and 2-benzothiazolyl. Group),

  A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, n -Octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 4-tert-butyl) Phenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group), hetero Ring oxy group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Heterocyclic oxy group, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, carbon A substituted or unsubstituted arylcarbonyloxy group of formula 6 to 30, for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group), carbamoyloxy group (preferably Is a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n- Octylaminocarbonyloxy group, -N-octylcarbamoyloxy group), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, p -N-hexadecyloxyphenoxycarbonyloxy group),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group; , Anilino group, N-methyl-anilino group, diphenylamino group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or Unsubstituted arylcarbonylamino group, for example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group), aminocarbonylamino group (preferably substituted or unsubstituted amino acid having 1 to 30 carbon atoms) Carbonylamino group, for example, carbamoylamino group, N, N-dimethylamino Sulfonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonyl) Amino group, tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) A carbonylamino group, such as a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, an mn-octyloxyphenoxycarbonylamino group, a sulfamoylamino group (preferably carbon 0-30 substituted or unsubstituted sulfamoylamino groups such as sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group), alkyl and arylsulfonylamino groups (Preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group),

  A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group or an n-hexadecylthio group), an arylthio group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). A substituted arylthio group such as phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2 -Benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- ( 3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, -Acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) An alkylsulfinyl group, a 6-30 substituted or unsubstituted arylsulfinyl group such as a methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably having a carbon number) 1-30 substituted or unsubstituted alkylsulfonyl groups, 6-30 substituted or unsubstituted arylsulfonyl groups (eg, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group),

  An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as an acetyl group or a pivaloylbenzoyl group), Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxy Carbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl Base Preferably, the substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (Methylsulfonyl) carbamoyl group),

  Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl group, dioctyl Oxyphosphinyl group, diethoxyphosphinyl group), phosphinyloxy group (preferred Or a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group, or a phosphinylamino group (preferably having a carbon number) 2-30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, silyl groups (preferably substituted or unsubstituted groups having 3 to 30 carbon atoms) Silyl group, for example, trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethylsilyl group).

  Among the above-mentioned substituents, those having a hydrogen atom may be substituted with the above-mentioned group after removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

  Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.

Preferred compounds of the formulas (IV) to (VI) are
R ¹¹ is a methyl group,
R ²¹ and R ²² are both hydrogen atoms,
R ¹² is an alkyl group having 3 or more carbon atoms,
L ³ is a single bond, —O—, —CO—, —NR—, —SO ₂ NR—, —NRSO ₂ —, —CONR—, —NRCO—, —COO—, —OCO—, and an alkynylene group (R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group, preferably a methyl group or a hydrogen atom, more preferably a hydrogen atom).
L ⁴ is —O— or —NR— (R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group; preferably a hydrogen atom).
Ar ⁴ is an arylene group,
The compound whose n is 3-6 is mentioned.

  Hereinafter, the compound represented by formula (V) or formula (VI) will be described in detail with specific examples, but the present invention is not limited to the following specific examples.

The compound represented by the formula (III) can be synthesized by first synthesizing a substituted benzoic acid and then by a general ester reaction or amidation reaction of the substituted benzoic acid and a phenol derivative or an aniline derivative to form an ester bond or an amide bond. Any reaction may be used as long as it is a reaction. For example, a method of converting a substituted benzoic acid to an acid halide and then condensing it with a phenol derivative or aniline derivative, a method of dehydrating condensation of a substituted benzoic acid and a phenol derivative or aniline derivative using a condensing agent or catalyst, etc. It is done.
In view of the production process and the like, a method in which a substituted benzoic acid is functionally converted to an acid halide and then condensed with a phenol derivative or an aniline derivative is preferable.

  Reaction solvents include hydrocarbon solvents (preferably toluene and xylene), ether solvents (preferably dimethyl ether, tetrahydrofuran, dioxane, etc.), ketone solvents, ester solvents, acetonitrile, dimethylformamide, dimethyl Acetamide or the like can be used. These solvents may be used alone or in admixture of several kinds, and preferred reaction solvents are toluene, acetonitrile, dimethylformamide and dimethylacetamide.

The reaction temperature is preferably 0 to 150 ° C, more preferably 0 to 100 ° C, still more preferably 0 to 90 ° C, and particularly preferably 20 ° C to 90 ° C.
In this reaction, it is preferable not to use a base. When a base is used, either an organic base or an inorganic base may be used, preferably an organic base such as pyridine, tertiary alkylamine (preferably triethylamine, ethyldiisopropyl). Pyramine and the like).

  The compound represented by the formula (VI) can be synthesized by a known method. For example, in the case of a compound where n = 4, the following structure:

(In the formula, A represents a reactive group such as a hydroxyl group or a halogen atom, and R ¹¹ , R ¹² , R ¹³ , R ²¹ and R ²² are as described above.)
An intermediate obtained by subjecting a raw material compound having a reaction with a derivative having a reactive site such as a hydroxyl group or an amino group:

(In the formula, A ′ represents a reactive group such as a carboxyl group, and R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , Ar ⁴ and L ³ are as described above.)
2 molecules

(Wherein, B and B 'represent a hydroxyl group, a reactive group such as an amino group, Ar ⁴ and L ⁴ have the same meanings as Ar ^4, L ⁴ described above.)
It can be obtained by linking by one molecule. However, the synthesis method of the compound of the present invention is not limited to this example.

The content of the retardation increasing agent of the present invention represented by the above formulas (I) to (VI) with respect to 100 parts by mass of cellulose acylate is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, 3-15 mass% is the most preferable.
The retardation increasing agent of the present invention may be added to a cellulose acylate solution (dope) after being dissolved in an organic solvent such as alcohol, methylene chloride or dioxolane, or may be added directly to the dope composition.

  The retardation increasing agents represented by formulas (I) to (VI) can be used alone or in combination of two or more. In the present invention, the combined use of retardation increasing agents represented by formulas (I) to (VI) is also preferred.

(UV absorber)
The cellulose acylate film of the present invention preferably contains a UV absorber in addition to the retardation increasing agent.
Examples of the ultraviolet absorber used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. A benzotriazole-based compound with a low content is preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are preferably used. When the cellulose acylate film of the present invention is used as a protective film for a polarizing plate, the ultraviolet absorber is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less from the viewpoint of preventing deterioration of the polarizer and the liquid crystal, and the liquid crystal. From the viewpoint of display properties, those that absorb less visible light having a wavelength of 400 nm or more are preferred.

  Specific examples of the benzotriazole ultraviolet absorber useful in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert). -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2 -Methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2 ' Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy Examples include, but are not limited to, a mixture of -5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate. As commercially available products, TINUVIN 109, TINUVIN 171 and TINUVIN 326 (all manufactured by Ciba Specialty Chemicals) can be preferably used.

(Organic solvent)
The organic solvent used in the present invention is an ether having 3 to 12 carbon atoms, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12 carbon atoms, and a halogenated carbonization having 1 to 6 carbon atoms. It is preferable to include a solvent selected from hydrogen.
The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms is preferably within the above-described preferable range of carbon atoms of the solvent having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.
Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogen atoms substituted by halogen in the halogenated hydrocarbon is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.
Two or more organic solvents may be mixed and used.

(Deterioration inhibitor)
A degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the cellulose acylate film. The deterioration preventing agents are described in JP-A-3-199201, JP-A-51907073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared, and more preferably 0.01 to 0.2% by mass. When the addition amount is in the above range, the effect of the deterioration preventing agent is easily obtained, and the deterioration preventing agent bleeds out on the film surface. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

(Matting agent)
Moreover, it is preferable that microparticles | fine-particles are added to the cellulose acylate film of this invention as a mat agent.
The kind of fine particles is preferably an inorganic compound, and examples of the inorganic compound include fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, and tin oxide. In this, it is preferable that it is a compound containing a silicon atom, and the silicon dioxide microparticles | fine-particles which can make the haze (haze) of a film small are especially preferable.

  Examples of the silicon dioxide fine particles include AEROSIL-200, 200V, 300, R972, R972V, R974, R202, R812, R805, OX50, and TT600 manufactured by Aerosil Co., Ltd.

In the present invention, the average particle size of the fine particles in the dry film is preferably 100 nm to 500 nm, and more preferably 150 nm to 400 nm.
The average particle size of the fine particles in the film can be confirmed by taking and observing a cross-sectional photograph. When the particle size is within the above range, haze (haze) deterioration is unlikely to occur, failure in a wound state due to foreign matter is unlikely to occur, and the effect of improving the winding property is sufficient.

  In the case of fine particles, the primary particle size, the particle size after being dispersed in a solvent, and the particle size after being added to the film often change. It is to control the particle size formed by aggregation and aggregation with the ester.

  When the particle diameter immediately after being dispersed in the solvent is A and the average particle diameter in the film is B, it is preferable that A / B = 0.5 to 1.0. This change in particle size is caused by the fact that aggregation is easily promoted when fine particles are dispersed and then mixed with cellulose triacetate or other low molecular weight compounds (hydrophobizing agents, etc.) in a solvent. When A / B is in the above range, the average particle size in the film becomes more suitable, and thus the transparency of the film is improved and the films are less likely to stick to each other.

  In order to set A / B to 0.5 to 1.0, the compatibility of the fine particle dispersion solvent and the functional groups on the surface of the fine particles with the dispersion solvent, cellulose triacetate, and UV absorber is improved. Further, the fine particles can be achieved by adding to a dope in which cellulose ester is dissolved or a dope in which an ultraviolet absorber is dissolved, and then dispersing by applying shear. As the disperser used here, an ultrasonic disperser, a line mill, a homomixer, or the like is preferably used.

  In the present invention, the addition amount of the fine particles is 0.15 to 0.5% by mass, preferably 0.20 to 0.35% by mass of fine particles having an average particle diameter of 100 to 500 nm, based on the film. More preferably, it is 0.20-0.30 mass%.

For the dispersion of the fine particles, a composition in which the fine particles and the solvent are mixed is preferably treated with a high-pressure dispersion device. The high-pressure dispersion apparatus used for dispersion can be a high-pressure dispersion apparatus that creates special conditions such as high shear and high pressure by passing a composition in which fine particles and a solvent are mixed at high speed through a narrow tube. By treating with a high-pressure dispersion apparatus, for example, in a thin tube having a tube diameter of 1 to 2,000 μm, the maximum pressure condition inside the apparatus is preferably 100 kgf / cm ² or more, more preferably 200 kgf / cm ² or more. is there. Further, at that time, those having a maximum reaching speed of 100 m / second or more and those having a heat transfer speed of 100 kcal / hour or more are preferable.

  Examples of such a high-pressure dispersing device include an ultra-high pressure homogenizer (trade name: Microfluidizer) manufactured by Microfluidic Corporation or a nanomizer manufactured by Nanomizer, and others include a Manton Gorin type high-pressure dispersing device such as Izumi Food Machinery. A homogenizer manufactured by the company can be used.

The fine particles are dispersed in a solvent containing 25 to 100% by mass of a water-soluble solvent, and then diluted by adding a water-insoluble organic solvent 0.5 to 1.5 times with respect to the water-soluble solvent. Is mixed with a dope dissolved in a solvent.
Then, the mixed liquid is cast on a support, dried, and formed into a film to obtain a cellulose acylate film.

  Here, as the water-soluble solvent, lower alcohols are mainly used. Preferred examples of lower alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol and the like.

  Further, the water-insoluble solvent is not particularly limited, but it is preferable to use a solvent used when forming a film of cellulose acylate, and a solvent having a solubility in water of 30% by mass or less is used, which includes methylene chloride, Examples include chloroform and methyl acetate.

  The fine particles are dispersed in the solvent at a concentration of 1 to 30% by mass. It is preferable to disperse in the above range because the viscosity becomes an appropriate range. The concentration of the fine particles in the dispersion is preferably 5 to 25% by mass, more preferably 10 to 20% by mass.

[Manufacture of cellulose acylate film]
The cellulose acylate film of the present invention can be produced by a solvent cast method. In the solvent cast method, a film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.

  A cellulose acylate solution can be prepared by a general method comprising processing at a temperature of 0 ° C. or higher (ordinary temperature or high temperature). The solution can be prepared using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent.

  The amount of cellulose acylate is preferably adjusted so that it is contained in an amount of 10 to 40% by mass in the resulting solution. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).

The solution can be prepared by stirring cellulose acylate and an organic solvent at room temperature (0 to 40 ° C.). High concentration solutions may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil.
The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.

Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially. The container must be configured to allow stirring. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.
When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. Further, the entire container can be heated by providing a plate heater outside the container and piping to circulate the liquid.
It is preferable to provide a stirring blade inside the container and use this to stir. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.
Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in the container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, cellulose acylate can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acylate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.
In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent at room temperature while stirring. The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add said arbitrary additive in a mixture.

  The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). The mixture of the cellulose acylate and the organic solvent is solidified by cooling.

  The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1,000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acylate dissolves in the organic solvent. The temperature may be increased by simply leaving it at room temperature or in a warm bath.
The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1,000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. . The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. .
A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.
In addition, according to the measurement by a differential scanning calorimeter (DSC), the 20 mass% solution which melt | dissolved cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) in methyl acetate by the cooling dissolution method is. In the vicinity of 33 ° C., there exists a quasi-phase transition point between a sol state and a gel state, and a uniform gel state is obtained below this temperature. Therefore, it is necessary to keep this solution at a temperature equal to or higher than the pseudo phase transition temperature, preferably about 10 ° C. plus the gel phase transition temperature. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method. It is preferable to add a retardation increasing agent to the dope.
The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. The surface of the drum or band is preferably finished in a mirror state. The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less.

  About the drying method in the solvent cast method, U.S. Pat. Nos. 2,336,310, 2,367,603, 2,492,078, 2,492,977, 2,492,978, 2,607,704, 2,739,069, 2,739,070, British Patent Nos. 640731 and 736892, Japanese Patent Publication Nos. 45-4554, 49-5614, These are described in JP-A-60-176834, JP-A-60-203430, and JP-A-62-115035. Drying on the band or drum can be performed by blowing an inert gas such as air or nitrogen.

  The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 ° C. to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

  Two or more layers can be cast using the prepared cellulose acylate solution (dope) to form a film. In this case, it is preferable to produce a cellulose acylate film by a solvent cast method. The dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is in the range of 10 to 40%. The surface of the drum or band is preferably finished in a mirror state.

  When casting a plurality of cellulose acylate solutions of two or more layers, it is possible to cast a plurality of cellulose acylate solutions, from a plurality of casting openings provided at intervals in the direction of travel of the support. You may produce a film, casting and laminating the solution containing a cellulose acylate, respectively. For example, the methods described in JP-A-61-158414, JP-A-1-122419, and JP-A-11-198285 can be used. It can also be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, JP-A-61-104413, JP-A-61-158413, and JP-A-6-134933. The method described in each publication can be used. Further, a cellulose acylate film is disclosed in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high-low viscosity cellulose acylate solution is extruded simultaneously. A casting method can also be used.

Also, using two casting ports, the film formed on the support by the first casting port is peeled off, and the second casting is performed on the side that was in contact with the support surface to produce a film. You can also For example, the method described in Japanese Patent Publication No. 44-20235 can be mentioned.
As the cellulose acylate solution to be cast, the same solution may be used, or different cellulose acylate solutions may be used. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port. Furthermore, the cellulose acylate solution of the present invention can be cast simultaneously with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, an ultraviolet absorption layer, a polarizing layer, etc.).

  In the conventional single-layer solution, it is necessary to extrude a cellulose acylate solution having a high concentration and a high viscosity in order to obtain a necessary film thickness. In such a case, the stability of the cellulose acylate solution is poor and solid matter is generated, which often causes problems due to defects or poor flatness. As a solution to this problem, by casting a plurality of cellulose acylate solutions from the casting port, it is possible to extrude a highly viscous solution onto the support at the same time, improving the flatness and improving the planar film. Not only can be produced, but also the use of a concentrated cellulose acylate solution can reduce the drying load and increase the production speed of the film.

  These steps from casting to post-drying may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. The winder used for the production of the cellulose acylate film used in the present invention may be a commonly used winder such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress. It can be wound up by a take-up method.

(Stretching)
The cellulose acylate film of the present invention is preferably stretched uniaxially only in the width direction or biaxially in the width direction and the transport direction.
Methods for stretching in the width direction are described in, for example, JP-A-62-115035, JP-A-4-152125, JP-A-2842211, JP-A-298310, and JP-A-11-48271. Yes.

  The film is stretched at room temperature or under heating conditions. The heating temperature is preferably not higher than the glass transition temperature of the film. The film can be stretched by a treatment during drying, and is particularly effective when the solvent remains. In the case of stretching in the longitudinal direction, for example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. In the case of stretching in the width direction, the film can also be stretched by conveying while holding the width of the film with a tenter and gradually widening the width of the tenter. After the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine).

  Biaxial stretching includes simultaneous biaxial stretching and sequential biaxial stretching, but sequential biaxial stretching is preferred from the viewpoint of continuous production, and after casting the dope, the film is peeled off from the band or drum, After stretching in the width direction (longitudinal method), the film is stretched in the longitudinal direction (width direction).

  The preferred stretching ratio of the cellulose acylate film of the present invention is preferably 1.0 to 1.1 times, more preferably 1.02 to 1.07 times in the case of uniaxial stretching only in the width direction.

In the case of biaxial stretching, it is preferable that the stretching ratio in the transport direction and the width direction satisfy the relationship of the following formula (F).
(F) 0.01 <(stretching ratio in the vertical direction) − (stretching ratio in the parallel direction) <0.1
More preferably, 0.02 <(stretch ratio in the vertical direction) − (stretch ratio in the parallel direction) <0.08.
By adjusting to these ranges, Re of the film can be adjusted to a preferable range by canceling the orientation of the cellulose acylate molecular chain generated during transportation, and the surface shape can be greatly improved.

[Thickness of cellulose acylate film]
The thickness of the cellulose acylate film of the present invention is preferably from 10 μm to 90 μm, and more preferably from 20 μm to 80 μm.

[Elastic modulus of cellulose acylate film]
The elastic modulus of the cellulose acylate film correlates with the degree of freedom of movement of the cellulose acylate molecular chain in the film. The higher the elastic modulus, the smaller the degree of freedom of movement of the cellulose acylate molecular chain. Also, the diffusion rate of low molecular weight compounds such as water becomes small. The elastic modulus of the cellulose acylate film can be increased by increasing the crystallinity. Conversely, the addition of a compound that is highly compatible with cellulose reduces the elastic modulus. The elastic modulus of the cellulose acylate film can be determined by a tensile test.
Specifically, the sample is conditioned for 24 hours in an environment of 25 ° C. and 60% RH, and the elastic modulus is measured according to the method described in JIS K7127. Tensilon manufactured by A & D Co., Ltd. can be used as the tensile tester.

The cellulose acylate film of the invention, the elastic modulus of RH 25 ° C. 60% in either direction in the width direction or longitudinal direction, 250 kgf / mm ² or more 650 kgf / mm ² or less is preferable, 350 kgf / mm ² or more 550 kgf / More preferably, it is mm ² or less. When the elastic modulus is within the above range, the dimensional stability of the polarizing plate and the processing characteristics of the film are improved.

[Crystallinity of cellulose acylate film]
The degree of crystallinity of the film can be increased by various methods, but the crystallization can be effectively promoted by processing at a high temperature with a high residual solvent amount. Therefore, in the production of a cellulose acylate film, it is preferable to dry the film at a high temperature immediately after the film is peeled off from the band or drum. The drying temperature is preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 180 ° C. or lower, and most preferably 120 ° C. or higher and 160 ° C. or lower.
The amount of residual solvent effective for increasing crystallization varies depending on the combination of solvent types. For example, in the case of a methylene chloride / methanol mixed solvent system, the mass ratio of the mixed solvent to the cellulose acylate film is preferably 1% to 70%, more preferably 5% to 60%, and more preferably 10% to 50%. Most preferred. In the mixed solvent system of methylene chloride / methanol / n-butanol, it is preferably 20% or more and 90% or less, more preferably 30% or more and 80% or less, and most preferably 30% or more and 70% or less.
The crystallinity defined in the present invention is the sum of values obtained by subtracting the diffraction intensity at a Bragg angle 2θ = 14 ° from the diffraction peak intensity detected by X-ray diffraction measurement.
The crystallinity of the acylate film of the present invention is preferably 3,000 to 15,000, more preferably 4,000 to 12,000, and most preferably 5,000 to 9,000.

[Moisture content of cellulose acylate film]
The moisture content of the cellulose acylate film can be evaluated by measuring the equilibrium moisture content at a constant temperature and humidity. The equilibrium moisture content is calculated by measuring the moisture content of the sample that has reached equilibrium after being left at the temperature and humidity for 24 hours by the Karl Fischer method and dividing the moisture content (g) by the sample mass (g). .
The water content of the cellulose acylate film of the present invention at 25 ° C. and 80% RH is preferably 3.5% by mass or less, and more preferably 3.2% by mass or less.

[Moisture permeability]
The moisture permeability is calculated as the amount of moisture (g) that evaporates in 24 hours per 1 m ^{2 of} area by measuring the moisture permeability of each sample in accordance with the method described in JIS Z 0208. The moisture permeability is a film property closely related to the durability of the polarizing plate, and the durability of the polarizing plate can be improved by reducing the moisture permeability. In the cellulose acylate film of the present invention, the moisture permeability at 25 ° C. and 90% RH for 24 hours is preferably from 80 g / m ^{2 to} 250 g / m ² . More preferably, it is 100 g / m ² or more and 200 g / m ² or less.
The moisture permeability per 1 μm of the film is preferably 1 g / m ² or more and 3 g / m ² or less, more preferably 1.5 g / m ² or more and 2.8 g / m ² or less.
When the moisture permeability is in the above range, drying at the time of preparing the polarizing plate becomes appropriate, and water penetration from the outside world is reduced, so that the polarizing plate durability is improved.

The moisture permeability can be lowered by reducing the amount of water adsorbed and the diffusion rate of water in the film. The use of a hydrophobizing agent is particularly preferable because the amount of water adsorbed can be reduced without increasing the diffusion rate of water in the film. A method for increasing the crystallinity of the cellulose acylate film is also preferable because the amount of water adsorbed can be reduced without increasing the diffusion rate of water in the film.
Further, the moisture permeability can be lowered by stretching in the transport direction and / or the width direction during film formation and by densely aligning the molecular chains of cellulose acylate. Stretching can be uniaxial stretching or biaxial stretching.

[Hygroscopic expansion coefficient]
The hygroscopic expansion coefficient indicates the amount of change in the length of the sample when the relative humidity is changed at a constant temperature.
In order to prevent a frame-like transmittance increase in the polarizing plate durability test, the hygroscopic expansion coefficient of the cellulose acylate film is preferably 30 × 10 ⁻⁵ /% RH or less, and 15 × 10 ⁻⁵ /% RH. More preferably, it is more preferably 10 × 10 ⁻⁵ /% RH or less. Further, the hygroscopic expansion coefficient is preferably small, but usually a value of 1.0 × 10 ⁻⁵ /% RH or more.
The method for measuring the hygroscopic expansion coefficient is shown below. A sample having a width of 5 mm and a length of 20 mm is cut out from the cellulose acylate film, one end is fixed, and the sample is hung in an atmosphere of 25 ° C. and 20% RH (R0). A weight of 0.5 g is hung on the other end and left for 10 minutes to measure the length (L0). Next, with the temperature kept at 25 ° C., the humidity is set to 80% RH (R1), and the length (L1) is measured. The hygroscopic expansion coefficient is calculated by the following formula. The measurement is performed 10 samples for the same sample, and the average value is adopted.
Hygroscopic expansion coefficient [/% RH] = {(L1-L0) / L0} / (R1-R0)

In order to reduce the dimensional change due to moisture absorption, it is preferable to reduce the amount of residual solvent during film formation and to reduce the free volume in the polymer film.
A general method for reducing the residual solvent is to dry at a high temperature for a long time. However, if the time is too long, the productivity is naturally lowered. Therefore, the amount of the residual solvent with respect to the cellulose acylate film is preferably in the range of 0.01 to 1% by mass, more preferably in the range of 0.02 to 0.07% by mass, and 0.03 to 0%. The most preferable range is 0.05 mass%.
By controlling the amount of the residual solvent, a polarizing plate having optical compensation ability can be produced at low cost with high productivity.
The amount of residual solvent is measured using a gas chromatograph (GC18A, manufactured by Shimadzu Corporation) by dissolving a certain amount of sample in chloroform.

  In the solution casting method as described above, a film is produced using a solution (dope) in which a polymer material is dissolved in an organic solvent. Drying by the solution casting method is largely divided into drying on the drum (or band) surface and drying during film conveyance. When drying on the drum (or band) surface, it is preferable to dry slowly at a temperature that does not exceed the boiling point of the solvent being used (when the boiling point is exceeded, bubbles are formed). Moreover, it is preferable to dry at the time of film conveyance at the glass transition point +/- 30 degreeC of a polymer material, More preferably, it is +/- 20 degreeC.

As another method for reducing the dimensional change due to moisture absorption, it is preferable to add a compound having a hydrophobic group. The material having a hydrophobic group is not particularly limited as long as the material has a hydrophobic group such as an alkyl group or a phenyl group in the molecule.
The addition amount of the compound having a hydrophobic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.1 to 20% by mass with respect to the solution (dope) to be adjusted. preferable.

[Photoelasticity]
The photoelastic coefficient of the cellulose acylate of the present invention is preferably 60 × 10 ⁻⁸ cm ² / N or less, and more preferably 20 × 10 ⁻⁸ cm ² / N. The photoelastic coefficient can be obtained by an ellipsometer.
[Glass-transition temperature]
The glass transition temperature of the cellulose acylate of the present invention is preferably 120 ° C. or higher and 180 ° C. or lower, and more preferably 130 ° C. or higher and 160 ° C. or lower. The glass transition temperature is a temperature at which the base line derived from the glass transition of the film starts to change and a temperature at which it returns to the base line again when measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). Is obtained as an average value of.

[Surface treatment of cellulose acylate film]
The cellulose acylate film is preferably subjected to a surface treatment. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. It is also preferable to provide an undercoat layer as described in JP-A-7-333433.
From the viewpoint of maintaining the flatness of the film, in these treatments, the temperature of the cellulose acylate film is preferably Tg (glass transition temperature) or lower, specifically 150 ° C. or lower.
When using a cellulose acylate film as a transparent protective film of a polarizing plate, it is particularly preferable to carry out an acid treatment or an alkali treatment, that is, a saponification treatment for cellulose acylate, from the viewpoint of adhesiveness with a polarizer.

The surface energy of the cellulose acylate film is preferably 55 mN / m or more, and more preferably 60 mN / m or more and 75 mN / m or less. The surface energy of a solid can be determined by a contact angle method, a wet heat method, and an adsorption method as described in “Basics and Applications of Wetting” (issued by Realize 1989.12.10). In the case of the cellulose acylate film of the present invention, it is preferable to use a contact angle method.
Specifically, two kinds of solutions having known surface energies are dropped on a cellulose acylate film, and at the intersection of the surface of the droplet and the surface of the film, the angle formed between the tangent line drawn on the droplet and the film surface, The surface angle of the film can be calculated by defining the angle containing the droplet as the contact angle.

Hereinafter, the alkali saponification treatment will be specifically described as an example.
The alkali saponification treatment of the cellulose acylate film is preferably performed in a cycle in which the film surface is immersed in an alkali solution, neutralized with an acidic solution, washed with water and dried.
Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably in the range of 0.1 to 3.0N, and in the range of 0.5 to 2.0N. More preferably it is. The alkaline solution temperature is preferably in the range of room temperature to 90 ° C, more preferably in the range of 40 to 70 ° C.

(Polarizer)
The polarizing plate of the present invention is a polarizing plate in which a protective film is bonded to both sides of a polarizer, and at least one of the protective films is the above-described cellulose acylate film.

(Configuration of polarizing plate)
First, a protective film and a polarizer constituting the polarizing plate of the present invention will be described.
The polarizing plate of this invention may have an adhesive layer, a separate film, and a protective film as a component other than a polarizer and a protective film.

(1) Protective film The polarizing plate of the present invention has a total of two protective films, one on each side of the polarizer, and at least one is the cellulose acylate film of the present invention. Moreover, it is preferable that at least one of the two protective films has a function as a retardation film. Moreover, it is preferable that the elastic modulus ratio of the protective film on both sides of the polarizer satisfies the following formula (G).
(G)
0.75 <(elastic modulus of the protective film on the liquid crystal cell side) / (elastic modulus of the protective film on the air interface side) <1.33
More preferably,
85 <(elastic modulus of the protective film on the liquid crystal cell side) / (elastic modulus of the protective film on the air interface side) <1.2
It is. By adjusting the elastic modulus ratio within this range, the change in transmittance of the polarizing plate with temperature and humidity can be reduced.
When using the polarizing plate of this invention for a liquid crystal display device, it is preferable that at least one of the two polarizing plates arrange | positioned at the both sides of a liquid crystal cell is a polarizing plate of this invention.

(2) Polarizer The polarizer of the present invention is preferably composed of polyvinyl alcohol (PVA) and a dichroic molecule. However, as described in JP-A-11-248937, PVA and polyvinyl chloride are dehydrated, A polyvinylene polarizer in which a polyene structure is generated by dechlorination and oriented is also usable.

PVA is a polymer material obtained by saponifying polyvinyl acetate, but may contain components copolymerizable with vinyl acetate such as unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, and vinyl ethers. . In addition, modified PVA containing an acetoacetyl group, a sulfonic acid group, a carboxyl group, an oxyalkylene group, or the like can also be used.
The saponification degree of PVA is not particularly limited, but is preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% from the viewpoint of solubility and the like. The degree of polymerization of PVA is not particularly limited, but is preferably 1000 to 10,000, and particularly preferably 1500 to 5000.
The syndiotacticity of PVA is preferably 55% or more for improving durability as described in Japanese Patent No. 2978219, but 45 to 52.5% described in Japanese Patent No. 3317494 is also preferably used. it can.

After PVA is formed into a film, it is preferable to introduce a dichroic molecule to constitute a polarizer. As a method for producing a PVA film, a method of forming a film by casting a stock solution in which a PVA resin is dissolved in water or an organic solvent is generally preferably used. The concentration of the polyvinyl alcohol-based resin in the stock solution is usually 5 to 20% by mass, and a PVA film having a thickness of 10 to 200 μm can be produced by forming this stock solution by casting. The PVA film can be produced with reference to Japanese Patent No. 3342516, Japanese Patent Application Laid-Open No. 09-328593, Japanese Patent Application Laid-Open No. 2001-302817, and Japanese Patent Application Laid-Open No. 2002-144401.
The degree of crystallinity of the PVA film is not particularly limited. However, in order to reduce the average crystallinity (Xc) of 50 to 75% by mass described in Japanese Patent No. 3251073 and the in-plane hue variation, Japanese Patent Application Laid-Open No. 2002-2005 A PVA film having a crystallinity of 38% or less described in No. 236214 can be used.

The birefringence (Δn) of the PVA film is preferably small, and a PVA film having a birefringence of 1.0 × 10 ⁻³ or less described in Japanese Patent No. 3342516 can be preferably used. However, as described in JP-A-2002-228835, in order to obtain a high degree of polarization while avoiding cutting during stretching of the PVA film, the birefringence of the PVA film may be set to 0.02 or more and 0.01 or less. Alternatively, as described in JP-A-2002-060505, the value of (nx + ny) / 2-nz may be 0.0003 or more and 0.01 or less. The retardation (in-plane) of the PVA film is preferably from 0 nm to 100 nm, and more preferably from 0 nm to 50 nm. Moreover, 0 nm or more and 500 nm or less are preferable, and, as for Rth (film thickness direction) of a PVA film, 0 nm or more and 300 nm or less are more preferable.

In addition, the polarizing plate of the present invention includes a PVA film having a 1,2-glycol bond amount of 1.5 mol% or less described in Japanese Patent No. 3021494, 5 μm or more described in JP-A No. 2001-316492. PVA film having 500 or less optical foreign matter per 100 cm ² , PVA film having a hot water cutting temperature spot of 1.5 ° C. or less in the TD direction of the film described in JP-A-2002-030163, and glycerin Preferred is a PVA film formed from a solution in which 1 to 100 parts by mass of a trivalent to hexavalent polyhydric alcohol such as 1 to 100 parts by mass or a plasticizer described in JP-A 06-289225 is mixed in an amount of 15% by mass or more. Can be used.

  Although the film thickness before extending | stretching of a PVA film is not specifically limited, 1 micrometer-1 mm are preferable and 20-200 micrometers is especially preferable from a viewpoint of stability of film holding | maintenance and the uniformity of extending | stretching. As described in JP-A-2002-236212, a thin PVA film in which the stress generated when stretching 4 to 6 times in water is 10 N or less may be used.

Dichroic molecule I ₃ ^- or I ₅ ^- can be preferably used an iodine ion or a dichroic dye higher such. In the present invention, higher-order iodine ions are particularly preferably used. Higher-order iodine ions can be found in “Applications of Polarizing Plates” by Ryo Nagata, CMC Publishing and Industrial Materials, Vol. 28, No. 7, p. 39-p. As described in 45, PVA can be produced by immersing PVA in a solution obtained by dissolving iodine in an aqueous potassium iodide solution and / or an aqueous boric acid solution and adsorbing and orienting the PVA.

  When a dichroic dye is used as the dichroic molecule, an azo dye is preferable, and a bisazo dye and a trisazo dye are particularly preferable. The dichroic dye is preferably a water-soluble dye. For this reason, a hydrophilic substituent such as a sulfonic acid group, an amino group or a hydroxyl group is introduced into the dichroic molecule, so that a free acid, an alkali metal salt, an ammonium salt or an amine is introduced. It is preferably used as a salt.

  Specific examples of such dichroic dyes include C.I. I. Direct Red 37, Congo Red (C.I. Direct Red 28), C.I. I. Direct Violet 12, C.I. I. Direct Blue 90, C.I. I. Direct Blue 22, C.I. I. Direct Blue 1, C.I. I. Direct Blue 151, C.I. I. Benzidines such as Direct Green 1, C.I. I. Direct Yellow 44, C.I. I. Direct Red 23, C.I. I. Diphenylurea such as Direct Red 79, C.I. I. Stilbene series such as Direct Yellow 12, C.I. I. Dinaphthylamine type such as Direct Red 31, C.I. I. Direct Red 81, C.I. I. Direct Violet 9, C.I. I. Mention may be made of J acid systems such as Direct Blue 78.

  In addition, C.I. I. Direct Yellow 8, C.I. I. Direct Yellow 28, C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 87, C.I. I. Direct Yellow 142, C.I. I. Direct Orange 26, C.I. I. Direct Orange 39, C.I. I. Direct Orange 72, C.I. I. Direct Orange 106, C.I. I. Direct Orange 107, C.I. I. Direct Red 2, C.I. I. Direct Red 39, C.I. I. Direct Red 83, C.I. I. Direct Red 89, C.I. I. Direct Red 240, C.I. I. Direct Red 242, C.I. I. Direct Red 247, C.I. I. Direct Violet 48, C.I. I. Direct Violet 51, C.I. I. Direct Violet 98, C.I. I. Direct Blue 15, C.I. I. Direct Blue 67, C.I. I. Direct Blue 71, C.I. I. Direct Blue 98, C.I. I. Direct Blue 168, C.I. I. Direct Blue 202, C.I. I. Direct Blue 236, C.I. I. Direct Blue 249, C.I. I. Direct Blue 270, C.I. I. Direct Green 59, C.I. I. Direct Green 85, C.I. I. Direct Brown 44, C.I. I. Direct Brown 106, C.I. I. Direct Brown 195, C.I. I. Direct Brown 210, C.I. I. Direct Brown 223, C.I. I. Direct Brown 224, C.I. I. Direct Black 1, C.I. I. Direct Black 17, C.I. I. Direct Black 19, C.I. I. Direct Black 54 and the like are further disclosed in JP-A-62-70802, JP-A-1-161202, JP-A-1-172906, JP-A-1-172907, JP-A-1-183602, JP-A-1-248105, The dichroic dyes described in JP-A-1-265205 and JP-A-7-261024 can also be preferably used. In order to produce dichroic molecules having various hues, two or more of these dichroic dyes may be blended. When a dichroic dye is used, the adsorption thickness may be 4 μm or more as described in JP-A No. 2002-082222.

If the content of the dichroic molecule in the film is too small, the degree of polarization is low, and if it is too large, the single-plate transmittance is lowered. Therefore, the polyvinyl alcohol polymer constituting the film matrix is usually used. On the other hand, it is adjusted to a range of 0.01% by mass to 5% by mass.
A preferable film thickness of the polarizer is preferably 5 μm to 40 μm, and more preferably 10 μm to 30 μm. The ratio between the thickness of the polarizer and the thickness of the protective film described later is 0.01 ≦ A (polarizer film thickness) / B (protective film thickness) ≦ 0.16 described in JP-A No. 2002-174727. A range is also preferable.
The crossing angle between the slow axis of the protective film and the absorption axis of the polarizer may be any value, but is preferably parallel or an azimuth angle of 45 ± 20 °.

(Polarizing plate manufacturing process)
Next, the manufacturing process of the polarizing plate of this invention is demonstrated.
The production process of the polarizing plate in the present invention is preferably composed of a swelling process, a dyeing process, a hardening process, a stretching process, a drying process, a protective film bonding process, and a post-bonding drying process. The order of the dyeing step, the hardening step, and the stretching step may be arbitrarily changed, or several steps may be combined and performed simultaneously. Moreover, as described in Japanese Patent No. 3331615, washing with water after the hardening step can be preferably performed.

  In the present invention, it is particularly preferable to sequentially perform the swelling process, the dyeing process, the hardening process, the stretching process, the drying process, the protective film bonding process, and the drying process after bonding in the order described. An on-line surface inspection step may be provided during or after the above-described steps.

The swelling step is preferably carried out only with water, but as described in JP-A-10-153709, in order to stabilize optical performance and avoid wrinkling of the polarizing plate substrate in the production line, polarized light is used. It is also possible to manage the degree of swelling of the polarizing plate substrate by swelling the plate substrate with an aqueous boric acid solution.
Moreover, although the temperature and time of a swelling process can be defined arbitrarily, 10 to 60 degreeC and 5 to 2000 second are preferable.
For the dyeing step, the method described in JP-A-2002-86554 can be used. Further, as a dyeing method, not only immersion but any means such as application or spraying of iodine or a dye solution can be used. Further, as described in JP-A-2002-290025, iodine concentration, dye bath temperature, stretch ratio in the bath, and a method of dyeing while stirring the bath liquid in the bath may be used.

When higher-order iodine ions are used as the dichroic molecule, in order to obtain a high-contrast polarizing plate, it is preferable to use a solution obtained by dissolving iodine in an aqueous potassium iodide solution in the dyeing step. In this case, iodine in the iodine-potassium iodide aqueous solution is preferably 0.05 to 20 g / l, potassium iodide is 3 to 200 g / l, and the mass ratio of iodine and potassium iodide is preferably 1 to 2000. The dyeing time is preferably 10 to 1200 seconds, and the liquid temperature is preferably 10 to 60 ° C. More preferably, iodine is 0.5 to 2 g / l, potassium iodide is 30 to 120 g / l, the mass ratio of iodine and potassium iodide is 30 to 120, dyeing time is 30 to 600 seconds, and liquid temperature is 20-50 degreeC is good.
Further, as described in Japanese Patent No. 3145747, boron compounds such as boric acid and borax may be added to the dyeing solution.

  In the hardening step, it is preferable to immerse in the crosslinking agent solution or apply the solution to contain the crosslinking agent. Further, as described in JP-A-11-52130, the hardening process can be performed in several steps.

  As the cross-linking agent, those described in US Reissue Patent No. 232897 can be used, and as described in Japanese Patent No. 3357109, a polyhydric aldehyde may be used as a cross-linking agent in order to improve dimensional stability. However, boric acids are most preferably used. When boric acid is used as a crosslinking agent used in the hardening step, metal ions may be added to the boric acid-potassium iodide aqueous solution. Zinc chloride is preferable as the metal ion, but as described in JP 2000-35512 A, zinc halides such as zinc iodide, zinc sulfates and zinc acetates are used instead of zinc chloride. You can also.

  In the present invention, it is preferable to prepare a boric acid-potassium iodide aqueous solution to which zinc chloride has been added, and perform dura- tion by immersing the PVA film. Boric acid is preferably 1 to 100 g / l, potassium iodide is 1 to 120 g / l, zinc chloride is preferably 0.01 to 10 g / l, hardening time is preferably 10 to 1200 seconds, and liquid temperature is preferably 10 to 60 ° C. . More preferably, boric acid is 10 to 80 g / l, potassium iodide is 5 to 100 g / l, zinc chloride is 0.02 to 8 g / l, hardening time is 30 to 600 seconds, and liquid temperature is 20 to 50 ° C is preferable.

  For the stretching step, a longitudinal uniaxial stretching method as described in US Pat. No. 2,454,515, or a tenter method as described in JP-A-2002-86554 can be preferably used. A preferable draw ratio is 2 times or more and 12 times or less, and more preferably 3 times or more and 10 times or less. Moreover, the relationship between the draw ratio, the thickness of the original fabric and the thickness of the polarizer is described in JP-A No. 2002-040256 (polarizer film thickness / raw film thickness after bonding of the protective film) × (total draw ratio) > 0.17 or the relationship between the width of the polarizer when leaving the final bath and the width of the polarizer when bonding the protective film is 0.80 ≦ (protective film pasting) described in JP-A-2002-040247 It is also preferable to satisfy the following condition: polarizer width at the time / width of the polarizer when leaving the final bath) ≦ 0.95.

  As the drying step, a method known in JP-A-2002-86554 can be used, but a preferable temperature range is 30 ° C. to 100 ° C., and a preferable drying time is 30 seconds to 60 minutes. Further, as described in Japanese Patent No. 3148513, heat treatment is performed so that the fading temperature in water is 50 ° C. or higher, or as described in Japanese Patent Laid-Open Nos. 07-325215 and 07-325218. Aging in a temperature and humidity controlled atmosphere can also be preferably performed.

  A protective film bonding process is a process of bonding the both surfaces of the above-mentioned polarizer which went out of the drying process with two protective films. A method of bonding with a pair of rolls is preferably used so that the adhesive liquid is supplied immediately before bonding and the polarizer and the protective film are overlapped. In addition, as described in JP-A-2001-296426 and JP-A-2002-86554, the moisture content of the polarizer at the time of bonding is adjusted in order to suppress the groove-like unevenness of the record due to the stretching of the polarizer. It is preferable to do. In the present invention, a moisture content of 0.1% to 30% is preferably used.

  The adhesive between the polarizer and the protective film is not particularly limited, and examples thereof include PVA resin (including modified PVA such as acetoacetyl group, sulfonic acid group, carboxyl group, oxyalkylene group) and boron compound aqueous solution. PVA resin is preferable. The thickness of the adhesive layer is preferably 0.01 to 5 μm, and particularly preferably 0.05 to 3 μm after drying.

Moreover, in order to improve the adhesive force of a polarizer and a protective film, it is preferable to perform adhesion after surface-treating the protective film to make it hydrophilic. The surface treatment method is not particularly limited, and a known method such as a saponification method using an alkaline solution or a corona treatment method can be used. Further, an easy-adhesion layer such as a gelatin undercoat layer may be provided after the surface treatment. As described in JP-A-2002-267839, the contact angle of the protective film surface with water is preferably 50 ° or less.
The drying conditions after bonding are in accordance with the method described in JP-A-2002-86554, but the preferred temperature range is 30 ° C. to 100 ° C., and the preferred drying time is 30 seconds to 60 minutes. It is also preferable to perform aging in an atmosphere with temperature and humidity control as described in JP-A-07-325220.

The element content in the polarizer is as follows: iodine 0.1-3.0 g / m ² , boron 0.1-5.0 g / m ² , potassium 0.1-2.00 g / m ² , zinc 0-2. It is preferably 00 g / m ² . Further, the potassium content may be 0.2% by mass or less as described in JP-A No. 2001-166143, and the zinc content in the polarizer is described in JP-A No. 2000-035512. It is good also as 0.04 mass%-0.5 mass%.

  As described in Japanese Patent No. 3323255, in order to increase the dimensional stability of the polarizing plate, an organic titanium compound and / or an organic zirconium compound is added and used in any of the dyeing process, stretching process and hardening process And at least 1 type of compound chosen from the organic titanium compound and the organic zirconium compound can also be contained. A dichroic dye may be added to adjust the hue of the polarizing plate.

(Characteristics of polarizing plate)
(1) Transmittance and degree of polarization The preferred single plate transmittance of the polarizing plate of the present invention is 42.5% or more and 49.5% or less, more preferably 42.8% or more and 49.0% or less. The transmittance is defined by Equation 3. A preferable range of the degree of polarization defined by Formula 4 is 99.900% or more and 99.999% or less, and more preferably 99.940% or more and 99.995% or less. A preferable range of the parallel transmittance is 36% or more and 42% or less, and a preferable range of the orthogonal transmittance is 0.001% or more and 0.05% or less. A preferable range of the dichroic ratio defined by Formula 5 is 48 or more and 1215 or less, and more preferably 53 or more and 525 or less.
The above-described transmittance is defined based on JISZ8701.

ここで、Ｋ、Ｓ（λ）、ｙ（λ）、τ（λ）は以下の通りである。

Here, K, S (λ), y (λ), and τ (λ) are as follows.

Ｓ（λ）：色の表示に用いる標準光の分光分布
ｙ（λ）：ＸＹＺ系における等色関数
τ（λ）：分光透過率
偏光度は下記式４で定義される。

S (λ): Spectral distribution of standard light used for color display y (λ): Color matching function in XYZ system τ (λ): Spectral transmittance The degree of polarization is defined by the following equation (4).

また、二色性比は下記式５で定義される。

The dichroic ratio is defined by the following formula 5.

The iodine concentration and the single plate transmittance may be within the ranges described in JP-A No. 2002-258051.
The parallel transmittance may be small in wavelength dependency as described in Japanese Patent Application Laid-Open Nos. 2001-083328 and 2002-022950. The optical characteristics when the polarizing plates are arranged in crossed Nicols may be in the range described in Japanese Patent Laid-Open No. 2001-091136, and the relationship between parallel transmittance and orthogonal transmittance is disclosed in Japanese Patent Laid-Open No. 2002-174728. It may be within the range described.

  As described in Japanese Patent Application Laid-Open No. 2002-221618, the standard deviation of the parallel transmittance every 10 nm when the light wavelength is between 420 and 700 nm is 3 or less, and the light wavelength is between 420 and 700 nm. The minimum value of (parallel transmittance / orthogonal transmittance) every 10 nm may be 300 or more.

  The parallel transmittance and the orthogonal transmittance at a wavelength of 440 nm of the polarizing plate, the parallel transmittance, the parallel transmittance and the orthogonal transmittance at a wavelength of 550 nm, and the parallel transmittance and the orthogonal transmittance at a wavelength of 610 nm are disclosed in JP-A No. 2002-258042 and JP-A No. The range described in 2002-258043 can also be preferably performed.

(2) Hue The hue of the polarizing plate of the present invention is preferably evaluated using the lightness index L ^* and the chromaticness index a ^* and b ^* in the L ^* a ^* b ^* color system recommended as the CIE uniform perceptual space. Is done.
L ^* , a ^* , and b ^* are described in, for example, Color Engineering, published by Tokyo Denki University Press.
L ^* , a ^* , and b ^* are defined by Equation 6 using X, Y, and Z described above.

Here, X ₀ , Y ₀ , and Z ₀ represent tristimulus values of the illumination light source. In the case of standard light C, X ₀ = 98.072, Y ₀ = 100, Z ₀ = 118.225, and standard light D _In the case of ₆₅ , X ₀ = 95.045, Y ₀ = 100, Z ₀ = 108.892.

The preferable range of a ^* for a single polarizing plate is −2.5 or more and 0.2 or less, and more preferably −2.0 or more and 0 or less. A preferable range of b ^* of the single polarizing plate is 1.5 or more and 5 or less, and more preferably 2 or more and 4.5 or less. The preferable range of a ^* of the parallel transmitted light of the two polarizing plates is −4.0 to 0, and more preferably −3.5 to −0.5. The preferred range of b ^* of the parallel transmitted light of the two polarizing plates is 2.0 or more and 8 or less, more preferably 2.5 or more and 7 or less. The preferable range of a ^* of the orthogonally transmitted light of the two polarizing plates is −0.5 or more and 1.0 or less, and more preferably 0 or more and 2 or less. The preferable range of b ^* of the orthogonally transmitted light of the two polarizing plates is −2.0 or more and 2 or less, and more preferably −1.5 or more and 0.5 or less.

The hue may be evaluated by the chromaticity coordinates (x, y) calculated from the aforementioned X, Y, and Z. For example, the chromaticity (x _p , y _p ) of the parallel transmitted light of the two polarizing plates. And the chromaticity (x _c , y _c ) of the orthogonal transmitted light are within the ranges described in JP-A-2002-214436, JP-A-2001-166136, and JP-A-2002-169024, or the relationship between the hue and the absorbance. It can also be preferably performed within the range described in JP-A-2001-311827.

(3) Viewing angle characteristics When a polarizing plate is arranged in crossed Nicol and light with a wavelength of 550 nm is incident, when vertical light is incident, from a azimuth of 45 degrees with respect to the polarization axis, 40 degrees with respect to the normal line It is also preferable that the transmittance ratio and the xy chromaticity difference when the light is incident at an angle of within the range described in Japanese Patent Application Laid-Open Nos. 2001-166135 and 2001-166137. Further, as described in JP-A-10-068817, the light transmittance (T ₀ ) in the vertical direction of the polarizing plate laminate having the crossed Nicols arrangement and the light transmission in the direction inclined by 60 ° from the normal line of the laminate. The ratio (T ₆₀ / T ₀ ) to the rate (T ₆₀ ) is 10000 or less, or as described in JP-A No. 2002-139625, the polarizing plate is at an arbitrary angle from the normal to an elevation angle of 80 degrees. When natural light is incident, the transmittance difference of transmitted light within a wavelength range of 20 nm within the wavelength range of 520 to 640 nm of the transmission spectrum is set to 6% or less, or a film described in JP-A-08-248201 It is also preferable that the brightness difference of the transmitted light at an arbitrary place 1 cm above is within 30%.

(4) Durability (4-1) Wet heat durability As described in JP-A-2001-116922, light transmittance and polarization degree before and after standing in an atmosphere of 60 ° C. and 90% RH for 500 hours. It is preferable that the change rate of is 3% or less based on the absolute value. In particular, the change rate of the light transmittance is 2% or less, and the change rate of the polarization degree is preferably 1.0% or less, more preferably 0.1% or less based on the absolute value. Further, as described in JP-A-07-0777608, it is also preferred that the degree of polarization after standing at 80 ° C. and 90% RH for 500 hours is 95% or more and the single transmittance is 38% or more.

(4-2) Dry durability It is preferable that the light transmittance and the rate of change of the degree of polarization before and after standing in a dry atmosphere at 80 ° C. for 500 hours are also 3% or less based on absolute values. In particular, the change rate of the light transmittance is preferably 2% or less, and the change rate of the polarization degree is preferably 1.0% or less, more preferably 0.1% or less based on the absolute value.

(4-3) Other durability Further, as described in JP-A-06-167611, the shrinkage after standing at 80 ° C. for 2 hours is 0.5% or less, or the both sides of the glass plate are crossed. The x and y values after leaving the Nicol-arranged polarizing plate laminate in an atmosphere of 69 ° C. for 750 hours are within the ranges described in JP-A-10-068818, or an atmosphere of 80 ° C. and 90% RH. the change in spectral intensity ratio of the 105 cm ^-1 and 157cm ^-1 after 200 hours standing processing by Raman spectroscopy at medium, it is also preferable to fall within the range as described in JP-a-08-094834 and JP-a-09-197127 It can be carried out.

(5) Orientation degree The higher the degree of orientation of PVA, the better the polarization performance, but the range of 0.2 to 1.0 is preferable as the order parameter value calculated by means such as polarization Raman scattering or polarization FT-IR. It is. Further, as described in JP-A-59-133509, the difference between the orientation coefficient of the polymer segment in the entire amorphous region of the polarizer and the orientation coefficient of the occupied molecule (0.75 or more) is at least 0. 15, the orientation coefficient of the amorphous region of the polarizer is 0.65 to 0.85 as described in JP-A No. 04-204907, and the higher order iodine ions of I ₃ ⁻ and I ₅ ⁻ It is also preferable to set the degree of orientation to 0.8 to 1.0 as an order parameter value.

(6) Other properties As described in JP-A-2002-006133, the contraction force in the absorption axis direction per unit width when heated at 80 ° C. for 30 minutes is 4.0 N / cm or less, As described in 2002-236213, when the polarizing plate was placed under heating conditions of 70 ° C. for 120 hours, both the dimensional change rate in the absorption axis direction and the dimensional change rate in the polarization axis direction of the polarizing plate were It is also preferable to make it within ± 0.6%, or to set the moisture content of the polarizing plate to 3% by mass or less as described in JP-A-2002-090546. Further, as described in JP-A No. 2000-249832, the surface roughness in the direction perpendicular to the stretching axis is set to 0.04 μm or less based on the center line average roughness, or described in JP-A No. 10-268294. The refractive index n ₀ in the transmission axis direction is preferably made larger than 1.6, or the relationship between the thickness of the polarizing plate and the thickness of the protective film is preferably within the range described in JP-A-10-111411. be able to.

(Functionalization of polarizing plate)
The polarizing plate of the present invention includes an LCD viewing angle widening film, a retardation film such as a λ / 4 plate for application to a reflective LCD, an antireflection film for improving display visibility, a brightness enhancement film, It is preferably used as a functionalized polarizing plate combined with an optical film having functional layers such as a coat layer, a forward scattering layer, and an antiglare (antiglare) layer.

  One embodiment of the configuration in which the polarizing plate of the present invention and the above-described functional optical film are combined is shown in FIG. The functional optical film 3 may be bonded to the polarizer 2 through an adhesive layer as a protective film on one side of the polarizing plate 5 (FIG. 1A), and the protective films 1a and 1b are attached to both surfaces of the polarizer 2. The functional optical film 3 may be bonded to the provided polarizing plate 5 through the adhesive layer 4 (FIG. 1B). In the former case, an arbitrary transparent protective film may be used for the other protective film 1. Moreover, in the polarizing plate of this invention, it is also preferable to stick an optical functional layer to a protective film through an adhesion layer, and to set it as the structure of FIG. It is also preferable that the peel strength between the layers such as the functional layer and the protective film is 4.0 N / 25 mm or more described in JP-A No. 2002-311238. The functional optical film is preferably disposed on the liquid crystal module side according to the intended function, or on the side opposite to the liquid crystal module, that is, on the display side or the backlight side.

The functional optical film used in combination with the polarizing plate of the present invention will be described below.
(1) Optical Compensation Film The polarizing plate of the present invention includes TN (Twisted Nematic), IPS (In-Plane Switching), OCB (Optically Compensated Bend), VA (Vertically Aligned), ECB (Electrically Bold). It can be used in combination with the optical compensation film proposed for the mode.

The optical compensation film used in combination with the polarizing plate of the present invention is roughly divided into two.
First, a retardation film is bonded to the cell-side protective film via an adhesive or the like, and second, an optically anisotropic layer is provided on the cell-side protective film.
Furthermore, what laminated | stacked the 1st type and the 2nd type further can be used preferably.

First, an optical compensation film of a type in which a retardation film is bonded to a cell-side protective film via an adhesive or the like will be described.
As the retardation film, a stretched polymer film can be used. As the polymer film, polycarbonate, polyimide, and norbornene resin (Arton manufactured by JSR, Zeonoa manufactured by Nippon Zeon Co., Ltd., etc.) can be preferably used.
For stretching, either uniaxial stretching or biaxial stretching can be used depending on the target retardation.

The retardation of the retardation film of the present invention preferably satisfies the following formula (H).
(H)
Re / Rth ratio of the protective film on the liquid crystal cell side> Re / Rth ratio of the retardation film More preferably, the Re / Rth ratio of the protective film on the liquid crystal cell side> Re / Rth ratio of the retardation film + 10
It is.

Moreover, it is preferable that the moisture permeability of the retardation film of this invention satisfy | fills the relationship of following formula (J) with respect to the moisture permeability of the protective film of a cell side.
(J)
Water vapor transmission rate per unit thickness of the protective film on the liquid crystal cell side> Water vapor transmission rate per unit thickness of the retardation film More preferably,
Water vapor transmission rate per unit thickness of the protective film on the liquid crystal cell side> Water vapor transmission rate per unit thickness of the retardation film + 0.5
It is. The moisture permeability per unit thickness is obtained by introducing the moisture permeability (g / m ² ) measured under the temperature and humidity conditions of 25 ° C. and 90% for 24 hours by the method described in JIS Z 0208 with the thickness (μm) of the film. .
By adjusting the retardation and moisture permeability to the above relationship, an optical compensation film with a small change in viewing angle compensation effect due to temperature and humidity can be obtained.

Next, the type in which the optically anisotropic layer is provided on the cell-side protective film will be described.
The optically anisotropic layer comprises a cellulose acylate film as a polarizing plate protective film on the liquid crystal cell side, an alignment layer provided thereon, and an optically anisotropic layer comprising a liquid crystalline compound formed on the alignment layer. And the optically anisotropic layer is crosslinked by UV light irradiation.

  The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, or formation of a layer having a microgroup. Furthermore, an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. The rubbing treatment is preferably performed by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. It is preferable that the absorption axis direction and the rubbing direction of the polarizer are substantially parallel. As the polymer used for the alignment layer, polyimide, polyvinyl alcohol, a polymer having a polymerizable group described in JP-A-9-152509, and the like can be preferably used. The thickness of the alignment layer is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.

  The optically anisotropic layer preferably contains a liquid crystalline compound. As the liquid crystalline compound used in the present invention, either a discotic compound (discotic liquid crystal) or a rod-like compound can be preferably used. The discotic liquid crystal molecule has a disk-like core portion like the triphenylene derivative of D-1, and has a structure in which side chains extend radially therefrom. In order to impart stability over time, it is also preferable to further introduce a group that reacts with heat, light or the like. Preferred examples of the discotic liquid crystal are described in JP-A-8-50206.

  The discotic liquid crystal molecules are aligned almost parallel to the film plane with a pretilt angle in the rubbing direction in the vicinity of the alignment layer, and the discotic liquid crystal molecules are oriented so that they are perpendicular to the plane on the opposite air side. doing. The discotic liquid crystal layer as a whole has a hybrid alignment, and this layer structure can realize a wide viewing angle of a TN mode TFT-LCD.

  The rod-like liquid crystalline molecules are azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, Phenyl dioxanes, tolanes and alkenyl cyclohexyl benzonitriles are preferred. In addition to low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used.

The rod-like liquid crystalline molecule preferably has a polymerizable group, and more preferably has two polymerizable groups at both ends of the rod-like molecular structure. A preferable polymerizable rod-like liquid crystal molecule is represented by the following formula (VII).
(VII) Q1-L1-Cy1-L2- (Cy2-L3) _n -Cy3-L4-Q2
In the formula, Q1 and Q2 are each independently a polymerizable group; L1 and L4 are each independently a divalent linking group; L2 and L3 are each independently a single bond or a divalent group. Cy1, Cy2 and Cy3 are each independently a divalent cyclic group; and n is 0, 1 or 2.
The polymerizable group of Q1 and Q2 is preferably a functional group capable of addition polymerization reaction, ring-opening polymerization reaction or condensation polymerization reaction. Below, the example of a polymeric group is shown.

  The polymerizable group is more preferably a functional group capable of addition polymerization (eg, Q-1 to Q-7) or a functional group capable of ring-opening polymerization (eg, Q-8, Q-9). A functional group capable of polymerization reaction is more preferable, and an ethylenically unsaturated polymerizable group (eg, Q-1 to Q-6) is most preferable.

  The divalent linking groups in L1, L2, L3, and L4 are -O-, -S-, -CO-, -NR- (R is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms), two It is preferably selected from valent chain groups and combinations thereof. Below, the example of the bivalent coupling group which consists of a combination is shown. The left and right in the following examples may be reversed.

L-1: —CO—O—
L-2: —CO—NH—
L-3: —O—CO—O—
L-4: -Divalent chain group -O-
L-5: -Divalent chain group -CO-
L-6: -Divalent chain group -O-CO-
L-7: -Divalent chain group -CO-O-
L-8: -Divalent chain group -O-CO-O-
L-9: -O-divalent chain group -O-
L-10: -O-divalent chain group -CO-
L-11: -O-Divalent chain group -O-CO-
L-12: -O-divalent chain group -CO-O-
L-13: -O-divalent chain group -O-CO-O-
L-14: -CO-divalent chain group -CO-
L-15: -CO-divalent chain group -O-CO-
L-16: -CO-divalent chain group -CO-O-
L-17: -CO-divalent chain group -O-CO-O-
L-18: —CO—O—divalent chain group —O—CO—
L-19: -CO-O-divalent chain group -CO-O-
L-20: -CO-O-divalent chain group -O-CO-O-
L-21: -O-CO-divalent chain group -CO-O-
L-22: —O—CO—divalent chain group —O—CO—O—
L-23: -O-CO-O-divalent chain group -O-CO-O-

L-24: -Divalent chain group -O-Divalent chain group -O-
L-25: -Divalent chain group -O-Divalent chain group -CO-
L-26: -Divalent chain group -O-Divalent chain group -O-CO-
L-27: -Divalent chain group -O-Divalent chain group -CO-O-
L-28: -Divalent chain group -O-Divalent chain group -O-CO-O-

L-29: -O-divalent chain group -O-divalent chain group -O-
L-30: -O-divalent chain group -O-divalent chain group -CO-
L-31: -O-divalent chain group-O-divalent chain group-O-CO-
L-32: -O-divalent chain group -O-divalent chain group -CO-O-
L-33: -O-divalent chain group -O-divalent chain group -O-CO-O-
L-34: -CO-divalent chain group-O-divalent chain group-CO-
L-35: —CO—Divalent chain group—O—Divalent chain group—O—CO—
L-36: —CO—Divalent chain group—O—Divalent chain group—CO—O—
L-37: -CO-divalent chain group-O-divalent chain group-O-CO-O-
L-38: -CO-O-divalent chain group -O-divalent chain group -O-CO-
L-39: -CO-O-divalent chain group -O-divalent chain group -CO-O-
L-40: -CO-O-divalent chain group -O-divalent chain group -O-CO-O-

L-41: -O-CO-divalent chain group-O-divalent chain group-CO-O-
L-42: —O—CO—divalent chain group—O—divalent chain group—O—CO—O—
L-43: -O-CO-O-divalent chain group -O-divalent chain group -O-CO-O-

L-44: -Divalent chain group-S-Divalent chain group-O-
L-45: -Divalent chain group-S-Divalent chain group-CO-
L-46: -Divalent chain group-S-Divalent chain group-O-CO-
L-47: -Divalent chain group-S-Divalent chain group-CO-O-
L-48: -Divalent chain group-S-Divalent chain group-O-CO-O-

L-49: -O-divalent chain group-S-divalent chain group-O-
L-50: -O-divalent chain group-S-divalent chain group-CO-
L-51: -O-divalent chain group-S-divalent chain group-O-CO-
L-52: -O-divalent chain group-S-divalent chain group-CO-O-
L-53: -O-divalent chain group-S-divalent chain group-O-CO-O-
L-54: -CO-divalent chain group-S-divalent chain group-CO-
L-55: -CO-divalent chain group-S-divalent chain group-O-CO-
L-56: -CO-divalent chain group-S-divalent chain group-CO-O-
L-57: -CO-divalent chain group-S-divalent chain group-O-CO-O-

L-58: -CO-O-divalent chain group-S-divalent chain group-O-CO-
L-59: -CO-O-divalent chain group-S-divalent chain group-CO-O-
L-60: -CO-O-divalent chain group-S-divalent chain group-O-CO-O-
L-61: -O-CO-divalent chain group-S-divalent chain group-CO-O-
L-62: -O-CO-divalent chain group-S-divalent chain group-O-CO-O-
L-63: -O-CO-O-divalent chain group-S-divalent chain group-O-CO-O-

The divalent chain group is selected from the group consisting of an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group. An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferred, and an alkylene group or an alkenylene group is more preferred.
The alkylene group may have a branch. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.

The alkylene part of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent of the substituted alkylene group include a halogen atom.
The alkenylene group may have a branch. The alkenylene group has preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.

The alkenylene part of the substituted alkenylene group is the same as the above alkenylene group. Examples of the substituent of the substituted alkenylene group include a halogen atom.
The alkynylene group may have a branch. The alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.

The alkynylene part of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent of the substituted alkynylene group include a halogen atom.
Examples of the divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 1-methyltetramethylene, pentamethylene, hexamethylene, 1-methyltrimethylene and 2-methyltrimethylene.

The ring of the divalent cyclic group in Cy1, Cy2 and Cy3 is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 6-membered ring. Most preferably.
The ring possessed by the cyclic group may be a condensed ring. However, a single ring is preferable to a condensed ring.

  The ring that the cyclic group has is an aromatic ring, an aliphatic ring, or a heterocyclic ring. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocyclic ring include 1,3-dioxane ring, 1,3,2-dioxaborane ring, 2,4,7-trioxabicyclo [2.2.2] octane ring, pyridine ring and pyrimidine ring. .

  The cyclic group having a benzene ring is preferably 1,4-phenylene. The cyclic group having a naphthalene ring is preferably 1,5-naphthylene and 2,6-naphthylene. The cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene. The cyclic group having a 1,3-dioxane ring is preferably 1,3-dioxane-2,5-diyl. The cyclic group having a 1,3,2-dioxaborane ring is preferably 1,3,2-dioxaborane-2,5-diyl. The cyclic group having a 2,4,7-trioxabicyclo [2.2.2] octane ring is preferably 2,4,7-trioxabicyclo [2.2.2] octane-1,4-diyl. The cyclic group having a pyridine ring is preferably 2,5-pyridinediyl. The cyclic group having a pyrimidine ring is preferably 2,5-pyrimidinediyl.

  The cyclic group may have a substituent. Examples of the substituent include a halogen atom, cyano, nitro, an alkyl group having 1 to 5 carbon atoms, a halogen-substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, carbon An alkylthio group having 1 to 5 atoms, an acyl group having 1 to 5 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl, and the number of carbon atoms 2-6 alkyl-substituted carbamoyl groups and amide groups having 2-6 carbon atoms are included.

When n in the formula (VII) is 2, two L3 may be different, and two Cy2 may be different. n is preferably 1 or 2, and more preferably 1.
Examples of the polymerizable rod-like liquid crystalline molecule represented by the formula (VII) are shown below.

  The optically anisotropic layer is generally formed by applying a solution prepared by dissolving a liquid crystal compound and other compounds (for example, a polymerizable monomer and a photopolymerization initiator) in a solvent onto the alignment layer, drying, and then discotic nematic. After heating to the phase formation temperature, it is obtained by polymerization by irradiation with UV light or the like and further cooling. The nematic liquid crystal phase-solid phase transition temperature of the liquid crystal compound used in the present invention is preferably 70 to 300 ° C, particularly preferably 70 to 170 ° C.

In addition, the compound other than the liquid crystalline compound added to the optically anisotropic layer is compatible with the liquid crystalline compound, as long as the change in the preferred tilt angle is given to the liquid crystalline compound or the alignment is not hindered. Any compound can be used. Among these, additives for controlling the orientation on the air interface side such as polymerizable monomers (eg, compounds having vinyl group, vinyloxy group, acryloyl group and methacryloyl group), fluorine-containing triazine compounds, cellulose acetate, cellulose acetate Mention may be made of polymers such as pionate, hydroxypropylcellulose and cellulose acetate butyrate. These compounds are generally used in an amount of 0.1 to 50% by mass, preferably 0.1 to 30% by mass, based on the discotic compound.
The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

The retardation of the optically anisotropic layer of the present invention and the retardation of the protective film on the liquid crystal cell side preferably satisfy the following formula (I).
(I)
Re / Rth ratio of the protective film on the liquid crystal cell side> Re / Rth ratio of the optically anisotropic layer More preferably, Re / Rth ratio of the protective film on the liquid crystal cell side> Re / Rth ratio of the optically anisotropic layer + 10
It is.

Moreover, it is preferable that the water vapor transmission rate of the optically anisotropic layer of this invention satisfy | fills the relationship of following formula (K) with respect to the water vapor transmission rate of the protective film by the side of a cell.
(K)
Water vapor transmission rate per unit thickness of the protective film on the liquid crystal cell side> Water vapor transmission rate per unit thickness of the optically anisotropic layer More preferably,
Water vapor transmission rate per unit thickness of the protective film on the liquid crystal cell side> Water vapor transmission rate per unit thickness of the optically anisotropic layer + 0.5
It is. The moisture permeability per unit thickness is obtained by introducing the moisture permeability (g / m ² ) measured under the temperature and humidity conditions of 25 ° C. and 90% for 24 hours by the method described in JIS Z 0208 with the thickness (μm) of the film. .
By adjusting the retardation and moisture permeability to the above relationship, an optical compensation film with a small change in viewing angle compensation effect due to temperature and humidity can be obtained.

  In addition to the above, when the optical compensation film and the polarizing plate of the present invention are combined, for example, as described in JP-A-07-198942, the birefringence has an optical axis in the direction intersecting the plate surface. It is also preferable to laminate with a retardation plate exhibiting anisotropy, or to make the dimensional change rate of the protective film and the optically anisotropic layer substantially the same as described in JP-A No. 2002-258052. be able to. Further, as described in JP-A-12-258632, the moisture content of the polarizing plate bonded to the optical compensation film is 2.4% or less, or as described in JP-A-2002-267839. It is also preferable to make the contact angle of the optical compensation film surface with water 70 ° or less.

  As an optical compensation film for TN mode, Journal of the Japan Printing Society, Vol. 36, No. 3 (1999) p. 40-44, monthly display August issue (2002) p. No. 20-24, JP-A-4-229828, JP-A-6-75115, JP-A-6-214116, JP-A-8-50206, etc. are preferably used in combination with WV film (manufactured by Fuji Photo Film Co., Ltd.). The

  The IPS mode liquid crystal cell optical compensation film is used for optical compensation of liquid crystal molecules aligned in parallel to the substrate surface and improvement of viewing angle characteristics of the orthogonal transmittance of the polarizing plate during black display without an electric field. In the IPS mode, black is displayed when no electric field is applied, and the transmission axes of the pair of upper and lower polarizing plates are orthogonal. However, when observed from an oblique direction, the crossing angle of the transmission axes is not 90 °, and leakage light is generated, resulting in a decrease in contrast. In order to reduce the leakage light, the cellulose acylate film of the present invention is used as a protective film on the liquid crystal cell side, and a retardation film or an optically anisotropic layer on which Re is 200 nm or more and 350 nm or less and Rth is negative Is preferably provided.

  An optical compensation film for OCB mode liquid crystal cells is used to improve the viewing angle characteristics of black display by optically compensating the liquid crystal layer that is vertically aligned at the center of the liquid crystal layer by applying an electric field and tilted in the vicinity of the substrate interface. Is done. An optical compensation in which the cellulose acylate film of the present invention is used as a protective film on the liquid crystal cell side, and an optically anisotropic layer in which a discotic liquid crystalline compound as described in US Pat. No. 5,805,253 is hybrid-aligned is provided. Films are preferred for OCB mode liquid crystal cells.

  The VA mode liquid crystal cell optical compensation film improves the viewing angle characteristics of black display in a state in which liquid crystal molecules are vertically aligned with respect to the substrate surface when no electric field is applied. The cellulose acylate film of the present invention is used as a liquid crystal cell-side protective film, and on this, a norbornene-based resin film or a polycarbonate resin that has been given a phase difference by stretching is preferably used as an optical compensation film for VA. Can be used.

(2) Antireflection film The polarizing plate of the present invention can be used in combination with an antireflection film. For the anti-reflection film, either a film having a reflectance of about 1.5% only by applying a single layer of a low refractive index material such as a fluorine-based polymer, or a film having a reflectance of 1% or less using multilayer interference of a thin film is used. it can. In the present invention, a structure in which a low refractive index layer and at least one layer having a higher refractive index than that of the low refractive index layer (that is, a high refractive index layer and a middle refractive index layer) is laminated on a transparent support is preferably used. The In addition, Nitto Technical Report, vol. 38, no. 1, may, 2000, pages 26 to 28, JP-A No. 2002-301783, and the like can also be preferably used.
The refractive index of each layer satisfies the following relationship.
The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer. A transparent polymer film can be preferably used.

  The refractive index of the low refractive index layer is 1.20 to 1.55, preferably 1.30 to 1.50. The low refractive index layer is preferably used as an outermost layer having scratch resistance and antifouling properties. In order to improve the scratch resistance, it is also preferable to impart slipperiness to the surface using a material containing a silicone group or fluorine.

Examples of the fluorine-containing compound include paragraph numbers [0018] to [0026] of JP-A-9-222503, paragraph numbers [0019] to [0030] of JP-A-11-38202, and JP-A-2001-40284. The compounds described in paragraph Nos. [0027] to [0028] and JP-A No. 2000-284102 can be preferably used.
The silicone-containing compound is preferably a compound having a polysiloxane structure, but reactive silicone (eg, Silaplane (manufactured by Chisso Corporation), silanol group-containing polysiloxane at both ends (JP-A-11-258403), etc. An organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent may be cured by a condensation reaction in the presence of a catalyst (Japanese Patent Laid-Open No. 58-142958). Gazettes, 58-147483, 58-147484, JP-A-9-157582, 11-106704, JP-A-2000-117902, 2001-48590, 2002-2002. 53804).
The low refractive index layer has an average primary particle diameter of 1 to 150 nm such as fillers (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as additives other than the above. And a low refractive index inorganic compound, organic fine particles described in paragraphs [0020] to [0038] of JP-A No. 11-3820, silane coupling agents, slip agents, surfactants, and the like are also preferably included. be able to.

The low refractive index layer may be formed by a vapor phase method (vacuum vapor deposition method, sputtering method, ion plating method, plasma CVD method, etc.), but is preferably formed by a coating method because it can be manufactured at low cost. . As the coating method, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and micro gravure can be preferably used.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.

The medium refractive index layer and the high refractive index layer preferably have a constitution in which ultrafine particles of high refractive index having an average particle size of 100 nm or less are dispersed in a matrix material. Inorganic compound fine particles having a high refractive index include inorganic compounds having a refractive index of 1.65 or more, for example, oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and metal atoms thereof. A composite oxide or the like can be preferably used.
Such ultrafine particles may be obtained by treating the particle surface with a surface treatment agent (silane coupling agent, etc .: JP-A Nos. 11-295503, 11-153703, 2000-9908, anionic compounds or (Organic metal coupling agent: JP-A-2001-310432, etc.), core-shell structure with high refractive index particles as a core (JP-A-2001-166104, etc.) No. 153703, Patent No. US62010858B1, Japanese Patent Laid-Open No. 2002-27776069, etc.).

As the matrix material, conventionally known thermoplastic resins, curable resin films, and the like can be used, but JP-A-2000-47004, 2001-315242, 2001-31871, and 2001-296401. It is also possible to use a curable film obtained from a polyfunctional material described in a gazette or the like or a metal alkoxide composition described in JP-A-2001-293818 or the like.
The refractive index of the high refractive index layer is preferably 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, and more preferably 10 nm to 1 μm.
The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70.

  The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. Further, the strength of the film is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.

(4) Brightness improving film The polarizing plate of this invention can be used in combination with a brightness improving film. The brightness enhancement film has a function of separating circularly polarized light or linearly polarized light, and is disposed between the polarizing plate and the backlight, and reflects or scatters one circularly polarized light or linearly polarized light back to the backlight side. Re-reflected light from the backlight part partially changes the polarization state and partially transmits when re-entering the brightness enhancement film and the polarizing plate, so the light utilization rate is improved by repeating this process. The front luminance is improved to about 1.4 times. As the brightness enhancement film, an anisotropic reflection method and an anisotropic scattering method are known, and both can be combined with the polarizing plate of the present invention.

  In the anisotropic reflection system, a brightness enhancement film having anisotropy in reflectance and transmittance is known by laminating a uniaxially stretched film and an unstretched film in multiple layers and increasing the refractive index difference in the stretching direction. Multilayer film systems using the principle of dielectric mirrors (described in the specifications of WO95 / 17691, WO95 / 17692, WO95 / 17699) and cholesteric liquid crystal systems (European Patent No. 606940A2, Japanese Patent Laid-Open No. Hei 8- No. 271731) is known. DBEF-E, DBEF-D, and DBEF-M (all manufactured by 3M) are used as multi-layer brightness enhancement films using the principle of dielectric mirrors, and NIPOCS (Nitto Denko Corporation) as a cholesteric liquid crystal brightness enhancement film. )) Is preferably used in the present invention. For NIPOCS, see Nitto Giho, vol. 38, no. 1, may, 2000, pages 19 to 21 and the like.

Further, in the present invention, positive numbers described in the specifications of WO97 / 32223, WO97 / 32224, WO97 / 32225, WO97 / 32226, and JP-A-9-274108 and 11-174231 It is also preferable to use in combination with an anisotropic scattering type brightness enhancement film obtained by uniaxially stretching by blending an intrinsic birefringent polymer and a negative intrinsic birefringent polymer. As the anisotropic scattering system brightness enhancement film, DRPF-H (manufactured by 3M) is preferable.
The polarizing plate and the brightness enhancement film of the present invention are preferably used as an integrated type in which one of the polarizing film and the protective film of the polarizing plate is bonded via an adhesive.

(5) Other functional optical films The polarizing plate of the present invention further comprises a hard coat layer, a forward scattering layer, an antiglare (antiglare) layer, a gas barrier layer, a sliding layer, an antistatic layer, an undercoat layer, a protective layer, and the like. It is also preferable to use in combination with the provided functional optical film. These functional layers are also preferably used in combination with each other in the same layer as the antireflection layer in the above-mentioned antireflection film or the optically anisotropic layer in the viewing angle compensation film. These functional layers can be used by providing either one side or both sides of the polarizer side and the surface opposite to the polarizer (more air side surface).

(5-1) Hard coat layer The polarizing plate of the present invention is preferably combined with a functional optical film having a hard coat layer provided on the surface of the transparent support in order to impart mechanical strength such as scratch resistance. . When the hard coat layer is applied to the above-described antireflection film, it is particularly preferable to provide it between the transparent support and the high refractive index layer.
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of the curable compound by light and / or heat. The curable functional group is preferably a photopolymerizable functional group, and the hydrous functional group-containing organometallic compound is preferably an organic alkoxysilyl compound. As specific constituent compositions of the hard coat layer, for example, those described in JP-A Nos. 2002-144913, 2000-9908 and WO00 / 46617 can be preferably used.
The film thickness of the hard coat layer is preferably 0.2 to 100 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  As the material for forming the hard coat layer, a compound containing an ethylenically unsaturated group or a compound containing a ring-opening polymerizable group can be used, and these compounds can be used alone or in combination. Preferred examples of the compound containing an ethylenically unsaturated group include ethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Polyacrylates of polyols such as hexaacrylate; epoxy acrylates such as diacrylate of bisphenol A diglycidyl ether, diacrylate of hexanediol diglycidyl ether; obtained by reaction of polyisocyanate and hydroxyl group-containing acrylate such as hydroxyethyl acrylate Examples of preferred compounds include urethane acrylates. Moreover, as a commercially available compound, EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (above, Daicel UCB Co., Ltd. product), UV -6300, UV-1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

  Preferred examples of the compound containing a ring-opening polymerizable group include ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, glycerol triglycidyl ether as glycidyl ethers. Triglycidyl trishydroxyethyl isocyanurate, sorbitol tetraglycidyl ether, pentaerythritol tetraglycyl ether, polyglycidyl ether of cresol novolac resin, polyglycidyl ether of phenol novolac resin, etc. Celoxide 2021P, Celoxide 2081, Epoxide GT-301, Epolide GT-401, EHPE3150CE (above, Oxetane, OXT-121, OXT-221, OX-SQ, PNOX-1009 (above, manufactured by Toagosei Co., Ltd.), etc. Can be mentioned. In addition, a polymer of glycidyl (meth) acrylate or a copolymer of a monomer that can be copolymerized with glycidyl (meth) acrylate may be used for the hard coat layer.

  In the hard coat layer, fine particles of oxide such as silicon, titanium, zirconium, and aluminum are used to reduce curing shrinkage of the hard coat layer, improve adhesion to the substrate, and reduce curling of the hard coat treated article of the present invention. It is also preferable to add crosslinked fine particles such as crosslinked fine particles such as polyethylene, polystyrene, poly (meth) acrylic acid esters, polydimethylsiloxane, etc., and fine organic particles such as fine crosslinked rubber particles such as SBR and NBR. These crosslinked fine particles preferably have an average particle size of 1 nm to 20000 nm. Further, the shape of the crosslinked fine particles can be used without particular limitation, such as a spherical shape, a rod shape, a needle shape, or a plate shape. The addition amount of the fine particles is preferably 60% by volume or less, more preferably 40% by volume or less of the hard coat layer after curing.

  In the case of adding the inorganic fine particles described above, since the affinity with the binder polymer is generally poor, it contains a metal such as silicon, aluminum, titanium, and the alkoxide group, carboxylic acid group, sulfonic acid group, phosphonic acid group, etc. It is also preferable to perform a surface treatment using a surface treatment agent having a functional group of

  The hard coat layer is preferably cured using heat or active energy rays. Among them, active energy rays such as radiation, gamma rays, alpha rays, electron rays, and ultraviolet rays are more preferred, and safety and productivity are improved. In view of the above, it is particularly preferable to use electron beams and ultraviolet rays. In the case of curing with heat, in consideration of the heat resistance of the plastic itself, the heating temperature is preferably 140 ° C. or lower, more preferably 100 ° C. or lower.

(5-2) Forward scattering layer The forward scattering layer is used to improve the viewing angle characteristics (hue and luminance distribution) in the vertical and horizontal directions when the polarizing plate of the present invention is applied to a liquid crystal display device. In the present invention, a configuration in which fine particles having different refractive indexes are dispersed in a binder is preferable. The construction of JP-A No. 199809, JP-A No. 2002-107512 that defines the haze value as 40% or more can be used. In addition, in order to control the viewing angle characteristics of haze, the polarizing plate of the present invention is also preferably used in combination with “Lumisty” described in Sumitomo Chemical's technical report “Photofunctional Films” on pages 31-39. be able to.

(5-3) Antiglare layer The antiglare (antiglare) layer is used to scatter reflected light and prevent reflection. The antiglare function is obtained by forming irregularities on the outermost surface (display side) of the liquid crystal display device. The haze of the optical film having an antiglare function is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.
The method for forming irregularities on the film surface is, for example, a method of forming irregularities on the film surface by adding fine particles (for example, JP-A No. 2000-271878), relatively large particles (particle size 0.05-2 μm). ) Is added in a small amount (0.1 to 50% by mass) (for example, Japanese Patent Application Laid-Open Nos. 2000-281410, 2000-95893, 2001-100004, and 2001). No. 281407, etc.), a method of physically transferring the uneven shape onto the film surface (for example, as an embossing method, JP-A-63-278839, JP-A-11-183710, JP-A-2000-275401) Etc.) can be preferably used.

(Adhesive)
Next, the adhesive preferably used in the present invention will be described.
As the adhesive, an adhesive using a base polymer such as acrylic acid, methacrylic acid, butyl rubber, or silicone can be used. Although not particularly limited, (meth) acrylate base polymers such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, A copolymer base polymer using two or more of these (meth) acrylic acid esters is preferably used. In the pressure-sensitive adhesive, a polar monomer is usually copolymerized in these base polymers. Examples of the polar monomer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like, such as glycidyl (meth) acrylate.

  The pressure-sensitive adhesive usually contains a crosslinking agent. Crosslinking agents include those that generate divalent or polyvalent metal ions and carboxylate metal salts, those that form amide bonds with polyamine compounds, those that form ester bonds with polyepoxy compounds and polyols, polyisocyanate compounds and amides. Examples of these compounds include one that forms a bond, and these compounds are used as a cross-linking agent in one or more kinds and mixed with a base polymer.

  As for the thickness of the adhesive layer of this invention, 2-50 micrometers is preferable. It is a normal form that a separate film is bonded to the surface of the pressure-sensitive adhesive layer opposite to the polarizing plate in order to protect the pressure-sensitive adhesive layer. As the separate film, a polyester film that has been subjected to a release treatment with a silicone resin or the like is used. This separate film is peeled and removed at the time of bonding with a liquid crystal cell or another optical functional film.

(Liquid crystal display device using polarizing plate)
Next, a liquid crystal display device in which the polarizing plate of the present invention is used will be described.
FIG. 2 is an example of a liquid crystal display device in which the polarizing plate of the present invention is used.

  The liquid crystal display device shown in FIG. 2 includes a liquid crystal cell (15 to 19) and an upper polarizing plate 11 and a lower polarizing plate 22 that are disposed with the liquid crystal cell (15 to 19) interposed therebetween. The polarizing plate is sandwiched between a polarizer and a pair of transparent protective films, but is shown as an integrated polarizing plate in FIG. The liquid crystal cell includes a liquid crystal layer formed of an upper substrate 15 and a lower substrate 18 and liquid crystal molecules 17 sandwiched therebetween. The liquid crystal cell is different in the alignment state of liquid crystal molecules that perform ON / OFF display. However, the polarizing plate of the present invention can be used in any display mode regardless of the transmissive and reflective types.

  An alignment film (not shown) is formed on the surface of the substrates 15 and 18 in contact with the liquid crystal molecules 17 (hereinafter also referred to as “inner surface”), and by rubbing treatment or the like applied on the alignment film, The alignment of the liquid crystal molecules 17 in the state where no electric field is applied or the state where a low voltage is applied is controlled. Further, on the inner surfaces of the substrates 15 and 18, a transparent electrode (not shown) capable of applying an electric field to the liquid crystal layer made of the liquid crystal molecules 17 is formed.

The rubbing direction of the TN mode is applied in directions perpendicular to each other on the upper and lower substrates, and the magnitude of the tilt angle can be controlled by the strength and the number of rubbing times. The alignment film is formed by applying and baking a polyimide film. The magnitude of the twist angle (twist angle) of the liquid crystal layer is determined by the crossing angle of the upper and lower substrates in the rubbing direction and the chiral agent added to the liquid crystal material. Here, a chiral agent having a pitch of about 60 μm is added so that the twist angle becomes 90 °.
The twist angle is in the vicinity of 90 ° (85 to 95 °) in the case of a notebook computer, a personal computer monitor, and a liquid crystal display device for a television, and is 0 to 70 ° in the case of use as a reflective display device such as a mobile phone. Set. In the IPS mode and the ECB mode, the twist angle is 0 °. In the IPS mode, electrodes are disposed only on the lower substrate 8 and an electric field parallel to the substrate surface is applied. In the OCB mode, there is no twist angle and the tilt angle is increased, and in the VA mode, the liquid crystal molecules 17 are aligned perpendicular to the upper and lower substrates.

Here, the magnitude of the product Δnd of the thickness d of the liquid crystal layer and the refractive index anisotropy Δn changes the brightness during white display. Therefore, in order to obtain the maximum brightness, the range is set for each display mode.
In general, the crossing angle of the absorption axis 12 of the upper polarizing plate 11 and the absorption axis 23 of the lower polarizing plate 22 is generally perpendicular to obtain a high contrast. The crossing angle between the absorption axis 12 of the upper polarizing plate 11 of the liquid crystal cell and the rubbing direction of the upper substrate 15 varies depending on the liquid crystal display mode, but is generally set to be parallel or vertical in the TN and IPS modes. In OCB and ECB modes, it is often set to 45 °. However, the optimum value differs in each display mode for adjusting the color tone and viewing angle of the display color, and the present invention is not limited to this range.

  The liquid crystal display device in which the polarizing plate of the present invention is used is not limited to the configuration of FIG. 2, and may include other members. For example, a color filter may be disposed between the liquid crystal cell and the polarizer. In addition, the above-described viewing angle widening films 13 and 20 may be separately disposed between the liquid crystal cell and the polarizing plate. The polarizing plates 11 and 22 and the viewing angle widening films 13 and 20 may be arranged in a laminated form bonded with an adhesive, or a so-called integrated elliptical polarization using one of the liquid crystal cell side protective films for widening the viewing angle. It may be arranged as a plate.

  When the liquid crystal display device using the polarizing plate of the present invention is used as a transmission type, a backlight using a cold cathode or a hot cathode fluorescent tube, or a light emitting diode, a field emission element, or an electroluminescent element as a light source. Can be placed on the back. Further, the liquid crystal display device in which the polarizing plate of the present invention is used may be of a reflective type. In such a case, only one polarizing plate may be disposed on the observation side, and the back of the liquid crystal cell or under the liquid crystal cell. A reflective film is installed on the inner surface of the side substrate. Of course, a front light using the light source may be provided on the liquid crystal cell observation side.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to an Example.

[Example 1]
(Preparation of cellulose acylate film 1)
<Preparation of cellulose acylate solution>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution A.

(Cellulose acylate solution A composition)
Cellulose acetate having an acetylation degree of 2.80 100.0 parts by mass Triphenyl phosphate (plasticizer) 6.0 parts by mass Biphenyl phosphate (plasticizer) 3.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass

<Preparation of matting agent solution>
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution.
(Matting agent solution composition)
Silica particles having an average particle diameter of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2.0 parts by mass Methylene chloride (first solvent) 75.0 parts by mass Methanol (second solvent) 12.7 parts by mass Cellulose acylate solution A 10.3 parts by mass

<Preparation of retardation increasing agent solution>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution.
(Retardation raising agent solution composition)
Retardation increasing agent (I-2) 20.0 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Cellulose acylate solution A 12.8 parts by mass

  94.5 parts by mass of the cellulose acylate solution A, 1.3 parts by mass of the matting agent solution, and 4.2 parts by mass of the retardation increasing agent solution were mixed after filtration, and cast using a band casting machine. did. The film was peeled from the band with a residual solvent content of 35%, and the film was stretched transversely at a stretch ratio of 4% using a tenter under the condition of 125 ° C., and held at 140 ° C. for 30 seconds with the stretched width. Thereafter, the clip was removed and dried at 140 ° C. for 40 minutes to produce a cellulose acylate film. The resulting cellulose acylate film had a residual solvent amount of 0.2% and a film thickness of 65 μm.

(Production of cellulose acylate films 2 to 11)
The same as the cellulose acylate film 1 except that the type of cellulose acylate, the type of retardation increasing agent, the addition amount, the type of UV agent, the addition amount, and the draw ratio in the transport direction and width direction were changed to the contents shown in Table 1. Thus, cellulose acylate films 2 to 11 were produced.

  The chemical structures of the plasticizers A and B and the UV agents (UV absorbers) A to D used for producing the cellulose acylate film are shown below.

  The moisture permeability and retardation of the cellulose acylate film thus prepared were measured by the following methods. The results are shown in Table 2.

<Measurement of moisture permeability>
The moisture permeability of each sample was measured according to the method described in JIS Z 0208. The temperature and humidity conditions for the test are 25 ° C. and 90% RH.

<Measurement of optical properties>
Further, Re and Rth at 25 ° C. and 60% were measured by the following methods.
Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments), Re and Rth at a wavelength of 590 nm at 25 ° C. and 60% were measured.

[Example 2]
(Saponification treatment)
Cellulose acylate films 1 to 11 were immersed in an aqueous 1.5 N sodium hydroxide solution at 55 ° C. for 2 minutes. It wash | cleaned in the room temperature water-washing tub, and neutralized using 0.1 N sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. In this way, the surface of the cellulose acylate film was saponified.

[Example 3]
A polarizer was prepared by adsorbing iodine to the stretched polyvinyl alcohol film, and the cellulose acylate film 1 prepared in Example 1 was attached to both sides of the polarizer using a polyvinyl alcohol-based adhesive. The transmission axis of the polarizer and the slow axis of the cellulose acylate film were arranged in parallel. In this way, a polarizing plate (A) was produced.

[Example 4]
Polarizing plates (A) to (M) were prepared in the same manner as in Example 3 using combinations of cellulose acylate films shown in Table 3.
The average elastic modulus of the protective films of the polarizing plates (A) to (M) was measured by the following method. The results are shown in Table 3.

<Measurement of elastic modulus>
The sample was conditioned for 24 hours in an environment of 25 ° C. and 60% RH, and the elastic modulus was measured according to the method described in JIS K7127. Tensilon manufactured by A & D Co., Ltd. was used as the tensile tester.

[Example 5]
A retardation film obtained by biaxially stretching an Arton film manufactured by JSR Co., Ltd. was bonded to the cellulose acylate film 1 side of the polarizing plate (A) prepared in Example 4 with an adhesive. The retardation film used had Re of 62 nm and Rth of 25 nm. In this way, a polarizing plate (A) with a retardation film was produced [Example 6].
Regarding the polarizing plates (B) to (M), the same retardation film as in Example 5 was bonded in the same manner as in Example 5 to prepare polarizing plates (B) to (M) with retardation.

[Example 7]
[Production and evaluation of VA liquid crystal display device]
The liquid crystal display device of FIG. 3 was produced. That is, from the observation direction (upper), from the upper polarizing plate 30 comprising the cellulose acylate film 33 and the polarizer 34, the VA mode liquid crystal cell (upper substrate, liquid crystal layer, lower substrate) 31, the cellulose acylate film 33 and the polarizer 34. The lower polarizing plate 32 is laminated, and a backlight light source (not shown) is further arranged. In the following example, the polarizing plate (A) with a retardation film produced in Example 4 is used for the upper polarizing plate, and the polarizing plate (K) of the comparative example of the present invention is used for the lower polarizing plate.

<Production of liquid crystal cell>
The liquid crystal cell has a cell gap between substrates of 3.6 μm, and a liquid crystal material having negative dielectric anisotropy (“MLC6608”, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates. Prepared by forming a layer. The retardation of the liquid crystal layer (that is, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn) was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

The upper polarizing plate of the liquid crystal display device using the above vertical alignment type liquid crystal cell (FIG. 3) is the polarizing plate with retardation film (A) prepared in Example 4 so that the retardation film is on the liquid crystal cell side. For the lower polarizing plate, the polarizing plate (K) prepared in Example 3 was placed on the viewer side and the backlight side through an adhesive so that the cellulose acylate film 11 of the present invention was on the liquid crystal cell side. I stuck them one by one. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. In this way, a liquid crystal display device (A) was produced.
Furthermore, liquid crystal display devices (B) to (M) were produced in the same manner except that the upper polarizing plate was changed to polarizing plates (B) to (M) with retardation films.
The durability of the produced liquid crystal display device was evaluated by the following method. The results are shown in Table 4.

<Durability evaluation>
After the liquid crystal display device was continuously lit at a humidity of 40 ° C. and 90% RH for 200 hours, the area of the light leakage portion generated in the peripheral portion and the contrast of the central portion were evaluated.
(Light leakage)
The degree of light leakage was evaluated according to the following criteria.
A: Light leakage in an area of 5% or less of the whole B: Light leakage in an area of 5% or more and 10% or less of the whole C: Light leakage in an area of 10% or more and 20% or less of the whole D: 20% or more of the whole 40 Light leakage in area of less than% E: Light leakage in area of more than 40% of total (contrast)
The central part was observed from 30 ° to the left with BM-5 manufactured by TOPCON, and the contrast was measured.

  From the results of Table 4, it was found that the liquid crystal display device of the present invention is preferable because it does not deteriorate the image quality even when used for a long time under high humidity.

[Example 8]
<Saponification treatment>
On the cellulose acetate film 1 produced in Example 1, 5.2 ml / m ^{2 of the following} composition was applied and dried at 60 ° C. for 10 seconds. The surface of the film was washed with running water for 10 seconds, and air at 25 ° C. was blown to dry the film surface.
(Saponification solution composition)
Isopropyl alcohol 818 parts by weight Water 167 parts by weight Propylene glycol 187 parts by weight Potassium hydroxide 68 parts by weight Surfactant n-C ₁₆ H ₃₃ O (C ₂ H ₄ ) ₁₀ H 12 parts by weight

(Formation of alignment film)
On a saponified cellulose acylate film, a coating solution having the following composition was applied at 28 ml / m ² with a # 16 wire bar coater. Drying was performed with warm air of 60 ° C. for 60 seconds, and further with warm air of 90 ° C. for 150 seconds.
Next, the formed film was rubbed in a direction parallel to the longitudinal direction of the cellulose acylate film.

(Orientation film coating solution composition)
Modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde (crosslinking agent) 0.5 parts by weight

  The chemical structural formula of the modified polyvinyl alcohol used in the alignment film coating solution is shown below.

変性ポリビニルアルコール

Modified polyvinyl alcohol

(Formation of optically anisotropic layer)
On the alignment film, 41.01 g of a rod-like liquid crystalline compound (IV-6), 4.06 g of ethylene oxide modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.), cellulose acetate butyrate (CAB551-) 0.2, manufactured by Eastman Chemical Co., Ltd.) 0.90 g, cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co., Ltd.) 0.23 g, photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Co.) 1.35 g, A coating solution prepared by dissolving 0.45 g of a sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) in 102 g of methyl ethyl ketone was applied with a wire bar of # 3.6. This was heated in a constant temperature zone of 130 ° C. for 2 minutes to orient the discotic compound. Next, UV irradiation was performed for 1 minute using a 120 W / cm high-pressure mercury lamp in an atmosphere at 60 ° C. to polymerize the liquid crystalline compound. Then, it stood to cool to room temperature. Thus, an optically anisotropic layer was formed, and an optical compensation sheet (D-1) was produced.
The optically anisotropic layer measured at a wavelength of 546 nm had an Re of 43 nm and an Rth of 67 nm.
Further, the moisture permeability per unit was 15 g / m ² / μm. The moisture permeability of the optically anisotropic layer can be determined by measuring the change in moisture permeability of the film before and after the optically anisotropic coating.

Iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizer, and was attached to one side of the polarizer using a polyvinyl alcohol-based adhesive so that the cellulose acetate film of the present invention was on the polarizer side. The transmission axis of the polarizer and the slow axis of the optically anisotropic layer were arranged in parallel.
Further, a commercially available cellulose triacetate film (Fujitac TD80UF, manufactured by Fuji Photo Film Co., Ltd.) was saponified in the same manner as described above, and attached to the opposite side of the polarizer using a polyvinyl alcohol adhesive.

(Production of liquid crystal display device)
A pair of polarizing plates provided on a 20-inch liquid crystal display device (LC-20V1, manufactured by Sharp Corporation) using a TN type liquid crystal cell is peeled off, and instead of the polarizing plate produced above, an optical compensation sheet is used. One sheet was attached to the observer side and the backlight side through an adhesive so as to be on the liquid crystal cell side. The transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side were arranged so as to be orthogonal to each other.
It was found that the liquid crystal display device using the optical compensation sheet of the present invention does not cause display unevenness even when used for a long time under high humidity, and a good image can be obtained.

[Example 9]
(Preparation of cellulose acylate film 201)
<Preparation of cellulose acylate solution>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution 201.

(Composition of cellulose acylate solution 201)
Cellulose acetate having an acetylation degree of 2.80 100.0 parts by mass Triphenyl phosphate (plasticizer) 5.0 parts by mass Biphenyl phosphate (plasticizer) 3.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass

<Preparation of matting agent solution>
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution.
(Matting agent solution composition)
Silica particles having an average particle diameter of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2.0 parts by mass Methylene chloride (first solvent) 75.0 parts by mass Methanol (second solvent) 12.7 parts by mass Cellulose acylate solution 201 10.3 parts by mass

<Preparation of retardation increasing agent solution>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a retardation increasing agent solution.
(Retardation raising agent solution composition)
Retardation increasing agent (B-121) 10.0 parts by mass Retardation increasing agent (B-122) 10.0 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Parts 12.8 parts by mass of cellulose acylate solution 201

  94.5 parts by mass of the cellulose acylate solution 201, 1.3 parts by mass of the matting agent solution, and 4.2 parts by mass of the retardation increasing agent solution were mixed after filtration, and cast using a band casting machine. did. The film was peeled off from the band with a residual solvent content of 33%, and the film was stretched transversely at a stretch ratio of 4% using a tenter under the condition of 125 ° C., and held at 125 ° C. for 30 seconds with the stretched width. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film 201 of the present invention. The finished cellulose acylate film (201) had a residual solvent amount of 0.2% and a film thickness of 80 μm.

(Preparation of cellulose acylate films 202 to 204)
Cellulose acylate films 202 to 204 of the present invention were produced in the same manner except that the type and addition amount of the retardation increasing agent in the cellulose acylate film 201 were changed to those shown in Table 5.

(Preparation of cellulose acylate film 211)
<Preparation of cellulose acylate solution>
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acylate solution 211.

(Composition of cellulose acylate solution 211)
Cellulose acetate propionate with acetylation degree 2.0 and propionylation degree 0.8
100.0 parts by mass Triphenyl phosphate (plasticizer) 5.0 parts by mass Ethylphthalyl ethyl glycolate (plasticizer) 2.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Ethanol (second solvent) 60.0 parts by mass

<Preparation of matting agent solution>
The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution.
(Matting agent solution composition)
Silica particles having an average particle diameter of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2.0 parts by mass Methylene chloride (first solvent) 75.0 parts by mass Ethanol (second solvent) 12.7 parts by mass Cellulose acylate solution 211 10.3 parts by mass

<Preparation of UV absorber solution>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare an ultraviolet absorber solution.
(Retardation raising agent solution composition)
UV agent A 10.0 parts by weight UV agent B 10.0 parts by weight Methylene chloride (first solvent) 58.4 parts by weight Ethanol (second solvent) 8.7 parts by weight Cellulose acylate solution A 12.8 parts by weight

  96.6 parts by mass of the cellulose acylate solution A, 1.3 parts by mass of the matting agent solution, and 2.1 parts by mass of the retardation increasing agent solution were mixed after filtration, and cast using a band casting machine. did. The film was peeled off from the band with a residual solvent content of 30%, and the film was stretched transversely at a stretch ratio of 4% using a tenter under the condition of 130 ° C., and held at 130 ° C. for 30 seconds with the stretched width. Thereafter, the clip was removed and dried at 130 ° C. for 40 minutes to produce a cellulose acylate film 211. The resulting cellulose acylate film 211 had a residual solvent amount of 0.3% and a film thickness of 115 μm.

<Measurement of optical properties>
Re and Rth at 25 ° C. and 60% were measured by an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments). The results are shown in Table 6.

[Example 10]
(Preparation of polarizing plates 201-204 and 211)
Polarizing plates 201 to 204 and a polarizing plate 211 were produced by the same treatment as in Examples 2 and 3 using the cellulose acylate films 201 to 204 and 211 produced in Example 9.

[Example 11]
(Preparation of polarizing plate 201-A)
A stretched arton film (Re (590) = 100, Rth (590) = 117 nm) is attached to the cellulose acylate film 201 side of the present invention of the polarizing plate 201 produced in Example 10 by using an adhesive, and polarizing plate 201- A was produced. In addition, it bonded together so that the transmission axis of a polarizing plate and the slow axis of a stretched arton film might become parallel.

(Production of polarizing plates 202-A to 204-A and 211-A)
In the same manner as the polarizing plate 201-A, the stretched Arton films were bonded to the polarizing plates 202 to 204 and 211 to prepare polarizing plates 202-A to 204-A and 211-A.

[Example 12]
(Production of liquid crystal display device)
For the upper polarizing plate of the liquid crystal display device of Example 7 (FIG. 3), the polarizing plate (201-A) with a stretched Arton film produced in Example 11 is used as the lower polarization so that the stretched Arton film is on the liquid crystal cell side. Commercially available polarizing plates (HLC2-5618 manufactured by Sanlitz) were attached to the plate one by one on the viewer side and the backlight side via an adhesive. The crossed Nicols were arranged so that the transmission axis of the polarizing plate on the viewer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. In this way, a liquid crystal display device 401 was produced.
Further, liquid crystal display devices 402 to 405 were produced in the same manner except that the upper polarizing plate was changed to polarizing plates with a stretched Arton film (202-A) to (204-A) and (211-A).

[Example 13]
(Change in color viewing angle)
With respect to the liquid crystal display devices 401 to 405 produced in Example 12, the change in hue between an azimuth angle of 0 ° and an azimuth angle of 80 ° at a polar angle of 60 ° was measured by Ezcontrast manufactured by ELDIM, and the color on the xy chromaticity diagram Absolute values Δx and Δy of the taste change were obtained.
The results are shown in Table 7.

  From the results shown in Table 7, it was found that the polarizing plate using the optical compensation sheet of the present invention is preferable because it has little change in color depending on the viewing angle when incorporated in a liquid crystal display. In particular, the liquid crystal display devices 401 to 404 using the cellulose acylate films 201 to 204 in which the wavelength dispersion of Rth satisfies the relationship of the above formulas (B) and (C) are preferable because the color change due to the viewing angle is particularly small.

FIG. 1 is an example of a configuration in which the polarizing plate of the present invention and a functional optical film are combined. FIG. 2 is an example of a liquid crystal display device in which the polarizing plate of the present invention is used. FIG. 3 is a schematic view showing an example of the liquid crystal display device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 1a, 1b Protective film 2 Polarizer 3 Functional optical film 4 Adhesive layer 5 Polarizing plate 11 Upper polarizing plate 12 Upper polarizing plate Absorption axis 13 Upper viewing angle widening film 14 Upper viewing angle widening film orientation control direction 15 On liquid crystal cell Electrode substrate 16 Upper substrate orientation control direction 17 Liquid crystal layer 18 Liquid crystal cell lower electrode substrate 19 Lower substrate orientation control direction 20 Lower viewing angle widening film 21 Lower viewing angle widening film orientation control direction 22 Lower polarizing plate 23 Lower polarizing plate absorption axis 30 Upper side Polarizing plate 31 VA mode liquid crystal cell 32 Lower polarizing plate 33 Cellulose acylate film 34 Polarizer

Claims (22)

Contains at least one retardation increasing agent,
The retardation increasing agent contains at least two compounds represented by the following formula (III),
In-plane retardation Re and thickness direction retardation Rth satisfy | fill the relationship of following formula (A), The cellulose acylate film characterized by the above-mentioned.
(A) 30 <Rth (590) / Re (590)
(Here, Re (λ) and Rth (λ) represent Re and Rth at a wavelength of λ nm, respectively.)

(In the formula, Ar ¹ and Ar ³ each independently represents an aryl group or a monovalent aromatic heterocyclic group, Ar ² represents an arylene group or a divalent aromatic heterocyclic group, and L ¹ and L ² each represent Independently represents a single bond or a divalent linking group, n represents an integer of 3 or more, and Ar ² and L ² may be the same or different, respectively.   The cellulose acylate film according to claim 1, wherein Re (590) is 0 nm or more and 5 nm or less.   The cellulose acylate film according to claim 1 or 2, wherein Rth (590) is 100 nm or more and 400 nm or less.   The cellulose acylate film according to any one of claims 1 to 3, wherein the retardation increasing agent is two kinds of compounds represented by the formula (III).   The cellulose acylate film according to claim 1, wherein the film thickness is 90 μm or less. The cellulose acylate according to any one of claims 1 to 5, wherein the substitution degree A of the acetyl group and the substitution degree B of the acyl group having 3 or more carbon atoms satisfy the following formulas (D) and (E): the film.
(D) 2.0 ≦ A + B ≦ 3.0
(E) 0 ≦ B ≦ 1.5   Said n is an integer of 3-7, The cellulose acylate film as described in any one of Claims 1-6. The Ar ² is an arylene group, The cellulose acylate film according to claim 1. The cellulose acylate film according to any one of claims 1 to 8, wherein the compound represented by the formula (III) is a compound represented by the following formula (IV).

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group, and R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom. Or Ar ⁴ represents an arylene group or divalent aromatic heterocyclic group, L ³ and L ⁴ each independently represent a single bond or a divalent linking group, and n represents an integer of 3 or more. In addition, Ar ⁴ and L ⁴ may be the same or different, respectively. The cellulose acylate film according to claim 9, wherein the compound represented by the formula (IV) is a compound represented by the following formula (VI).

(Wherein R ²¹ and R ²² each independently represent a hydrogen atom or a substituent, R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group, and L ³ and L ⁴ each independently represent Represents a single bond or a divalent linking group, Ar ⁴ represents an arylene group or a divalent aromatic heterocyclic group, n represents an integer of 3 or more, and L ⁴ and Ar ⁴ may be the same (However, R ¹¹ and R ¹² are different from each other, and the alkyl group represented by R ¹² does not include a hetero atom.) A cellulose acylate film comprising a step of preparing a solution containing cellulose acylate , a retardation increasing agent and a solvent, a step of casting the solution on a support, and a step of removing the solvent and drying to form a film. A manufacturing method comprising:
The cellulose as described in any one of Claims 1-10 which further includes the process extended | stretched by the magnification of 1.0 or more and 1.1 or less in the direction (henceforth width direction) perpendicular | vertical with respect to the conveyance direction at the time of film forming. A method for producing an acylate film. A cellulose acylate film comprising a step of preparing a solution containing cellulose acylate , a retardation increasing agent and a solvent, a step of casting the solution on a support, and a step of removing the solvent and drying to form a film. A manufacturing method comprising:
The method further includes a step of stretching simultaneously or sequentially in two directions, parallel and vertical, with respect to the transport direction during film formation, and the stretch ratio in the transport direction and the stretch ratio in the vertical direction satisfy the relationship of the following formula (F). The manufacturing method of the cellulose acylate film of any one of Claims 1-10.
Formula (F)
0.01 <(stretch ratio in the vertical direction) − (stretch ratio in the parallel direction) <0.1   A cellulose acylate film produced by the production method according to claim 11 or 12. A polarizing plate in which a protective film is bonded to both sides of a polarizer,
At least 1 sheet of this protective film is the cellulose acylate film as described in any one of Claims 1-10, 13, The polarizing plate characterized by the above-mentioned. The polarizing plate of Claim 14 with which elastic modulus ratio of the protective film of the both sides of a polarizer satisfy | fills following formula (G).
Formula (G)
0.75 <(elastic modulus of the protective film on the liquid crystal cell side) / (elastic modulus of the protective film on the air interface side) <1.33   The polarizing plate according to claim 14 or 15, wherein one or more retardation films are further laminated on the protective film on the liquid crystal cell side.   The polarizing plate as described in any one of Claims 14-16 which provided the optically anisotropic layer on the protective film by the side of a liquid crystal cell. The protective film on the liquid crystal cell side is the cellulose acylate film according to any one of claims 1 to 10, and Rth (590) / Re (590) of the retardation film on the protective film on the liquid crystal cell side. The polarizing plate according to claim 16, wherein the ratio satisfies the relationship of the following formula (H).
Formula (H)
Rth (590) / Re (590) ratio of the protective film on the liquid crystal cell side> Rth (590) / Re (590) ratio of the retardation film The protective film on the liquid crystal cell side is the cellulose acylate film according to any one of claims 1 to 10, and Rth (590) / Re () of the optically anisotropic layer on the protective film on the liquid crystal cell side. 590) The polarizing plate according to claim 17, wherein the ratio satisfies the relationship of the following formula (I).
Formula (I)
Rth (590) / Re (590) ratio of the protective film on the liquid crystal cell side> Rth (590) / Re (590) ratio of the optically anisotropic layer The protective film on the liquid crystal cell side is the cellulose acylate film according to any one of claims 1 to 10, and the water permeability per unit thickness of the retardation film on the protective film on the liquid crystal cell side is represented by the following formula: The polarizing plate according to claim 16 or 18, which satisfies the relationship (J).
Formula (J)
Water permeability per unit thickness of the protective film on the liquid crystal cell side> Water permeability per unit thickness of the retardation film The protective film on the liquid crystal cell side is the cellulose acylate film according to any one of claims 1 to 10, and the water permeability per unit thickness of the optically anisotropic layer on the liquid crystal cell side protective film is as follows. The polarizing plate of Claim 17 or 19 satisfy | filling the relationship of Formula (K).
Formula (K)
Water permeability per unit thickness of the protective film on the liquid crystal cell side> Water permeability per unit thickness of the optically anisotropic layer A liquid crystal display device having a liquid crystal cell and two polarizing plates arranged on both sides thereof,
At least 1 polarizing plate is a polarizing plate as described in any one of Claims 14-21, The liquid crystal display device characterized by the above-mentioned.

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